# Crown-Ether-Directed Assembly of One-Dimensional Silver(I) Coordination Polymers With Dramatically Enhanced Photoluminescence

Xiaojiao Yang, Xiao-lin Ye, Shu-han Bao, Dong-nan Yu, Wenya Jiang, Bintao Wu, Shuaiqi Wang, Kangzhou Wang, Tang Yang, Guozong Yue, et al.

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To cite this version:

Xiaojiao Yang, Xiao-lin Ye, Shu-han Bao, Dong-nan Yu, Wenya Jiang, et al., Crown-Ether-Directed Assembly of One-Dimensional Silver(I) Coordination Polymers With Dramatically Enhanced Photoluminescence. Aggregate, 2025, pp.e70092. 10.1002/agt2.70092. hal-05156877

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Distributed under a Creative Commons Attribution 4.0 International License
Crown-Ether-Directed Assembly of One-Dimensional Silver(I) Coordination Polymers
with Dramatically Enhanced Photoluminescence

Xiaojiao Yang,¹# Xiao-Lin Ye,¹# Shu-Han Bao,¹ Dong-Nan Yu,¹ Wenya Jiang,¹ Bintao Wu,¹
Shuaiqi Wang,¹ Kangzhou Wang,¹ Tang Yang,¹ Guozong Yue,² Samia Kahlal,³ Jean-Yves
Saillard,³ Jean-François Halet,³ Jianyu Wei,¹ and Kuan-Guan Liu*¹

¹Dr. X. Yang, X.-L. Ye, S.-H. Bao, D.-N. Yu, W. Jiang, Prof. Dr. B. Wu, Dr. S. Wang, Dr. K. Wang, Dr. T. Yang, Dr. J. Wei, Prof. Dr. K.-G. Liu
School of Materials and New Energy, State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021, P. R. China

E-mail: (jianyu.wei@nxu.edu.cn and liukuanguan@nxu.edu.cn)

²Dr. G. Yue
Institute of Materials China Academy of Engineering Physics, No. 9, Huafengxincun,
Jiangyou City, Sichuan Province, P. R. China

E-mail: (yueguozong@caep.cn)

³Dr. S. Kahlal, Prof. Dr. J.-Y. Saillard, Prof. Dr. J.-F. Halet
*Univ Rennes, CNRS, Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Institut des Sciences Chimiques de Rennes (ISCR), UMR 6226, F-35000 Rennes, France*

E-Mail: (jean-francois.halet@univ-rennes.fr)

#These authors contributed equally to this work.

**Keywords:** Silver(I), One Dimensional Coordination Polymer, Photoluminescence, Crown-Ether, Aggregations

**Abstract:** Two novel 18-crown-6-ether (18-C-6) directed one-dimensional silver(I) coordination polymers (1D Ag(I) CPs), formulated as {[(18-C-6)Ag(bpy)]·X}∞ and {[(18-C-6)Ag(pyz)]·X}∞ {bpy = 4,4'-bipyridine; pyz = pyrazine; X = BF4⁻ (Ia, IIa), CF3SO3⁻ (Ib, IIb)}, are prepared and structurally determined. The protection of the 18-C-6 macrocycle not only efficiently prevents intermolecular interactions within each 1D Ag(I)CP but also significantly enhances the rigidity of the chain structures, allowing these polymers to exhibit remarkable phosphorescence with intense green-light emission at room-temperature.

Moreover, IIa and IIb show enhanced photoluminescence quantum yields and aggregation-
induced emission properties, which can be attributed to their close-packed structure modes in
the crystalline states. Interestingly, upon mixing with commercial resin, IIa can serve as an
efficient and stable luminescent ink for 3D printing. The resulting printed structures
demonstrate exceptional irradiation stability, retaining their luminescence properties without
any quenching over a three-month period. This work not only provides a facile strategy to
prepare luminescent 1D Ag(I) CPs, but also shows the promise of their utilization in optical
devices.

**1. Introduction**

The growing demand for new materials with molecular-scale properties in the past few
decades has led to the rapid increase of one-dimensional (1D) nanostructures. ¹⁻⁵ Among them,
organometallic coordination polymers (OMCPs) have attracted great attention due to their
remarkable structure derived from various controllable coordination modes and efficient
electron transfer between metal centers and organic ligands. ⁶⁻⁸ This makes them promising
candidate materials for various applications including nano-electronics, ⁹ nano-devices,¹⁰
biomedicine,¹¹ dye-sensitized solar cells,¹² supercapacitor,¹³⁻¹⁴ and nano-photonics. ¹⁵ Coinage
metal(I) complexes with d¹⁰ electronic configurations are generally expected to show
photoluminescence (PL) with high intensity due to their large HOMO-LUMO gaps which
afford a substantial energy separation between their singlet ground state (S₁) and lowest triplet
state (T₁). ¹⁶⁻¹⁹ However, it is of note that a large part of coinage metal(I) complexes,
especially Ag(I) ones, are in fact weakly emitting or even non-luminescent, including at low
temperature (77 K). ²⁰⁻²⁴ Indeed, the emitting properties of this kind of Ag(I) complexes are
not only depending on the electronic characteristics of the Ag(I) centers, but are also affected
by their local environment, structural rigidity, intermolecular interactions, aggregation states,
etc. ²⁵⁻³⁴ Thus, constructing and controlling Ag(I) complexes with high photoluminescence
remains very challenging.
In general, the Ag(I) cation tends to linearly coordinate to two 2-electron neutral donor ligands to form a 14-electron ML₂ species such as, for instance, the diamine-silver(I) complex [Ag(NH₃)₂]⁺.³⁵ This kind of compounds hardly show any luminescence since, upon excitation, the energy is dissipated via vibrational relaxation of the rotatable ligands. One way to possibly trigger the luminescence of linear Ag(I) complexes is to aggregate the metal centers, by using ditopic bridging ligands such as 4,4'-bipyridine (bpy)³⁶⁻³⁸ or pyrazine (pyz),³⁹⁻⁴³ to form a 1D infinite structure with enhanced regularity and rigidity. But still, this is not enough and the linear chain-structured [Ag(bpy)]∞ or [Ag(pyz)]∞ coordination polymers (CPs) do not luminesce.⁴⁴⁻⁴⁷ Indeed, in the solid state, the 1D chains are not isolated from each other but easily interconnect to form complicated networks via the coordination of counterions, π...π stacking or argentophilic interactions,⁴⁴,⁴⁵ resulting in luminescence quenching (Figure 1). Therefore, the photoluminescence properties of the “true” 1D Ag(I) CPs are rarely explored.

One potential strategy to suppress intermolecular interactions and trigger the photoluminescence of non-luminescent [Ag(bpy)]∞ and [Ag(pyz)]∞ CPs is to isolate each Ag(I) center using protective macrocycles.⁴⁴⁻⁴⁷ Notably, 18-crown-6-ether (18-C-6) is a suitable candidate because its cavity size precisely matches the dimension of silver atoms, enabling multidentate coordination with Ag(I) centers. Herein, we report for the first time a crown-ether directed method to achieve the “true” 1D Ag(I) CPs ([Ag(bpy)]∞ and [Ag(pyz)]∞). In these CPs, each Ag(I) center is linearly coordinated to bpy or pyz ligands, and “nested” in an 18-crown-6-ether (18-C-6) macrocycle, leading to an infinite “Sugar-coated Haws”-like 1D structure (Figure 2). The obtained Ag(I) CPs show then dramatically enhanced room temperature phosphorescence and aggregation-induced emission (AIE). The protection of 18-C-6 prohibits any type of interaction between chains, making them well-separated and with enhanced regularity and rigidity (Figure 1). The structures, stability, and optical properties of
these novel CPs were further explored by various characterization tools and density functional
theory (DFT) calculations. The main results are reported and discussed here.

**2. Results and Discussion**

**2.1. Synthesis and General Characterization**

Four Ag(I) CPs were synthesized under similar solvothermal conditions. In brief, 18-C-6
was mixed with AgBF₄ or AgCF₃SO₃ in methanol solution, and after ultrasonic treatment for
5 min, a colorless solution was formed. Then, the bridging ligands (4,4'-bpy or pyz) were
added, under ultrasonication for 10-15 min to obtain a white turbid solution. The mixture was
then heated to 70 °C and kept for 20 h. After cooling to room temperature, colorless elongated
crystals of {[(18-C-6)Ag(bpy)]·X}∞ {X = BF₄⁻ (Ia), CF₃SO₃⁻ (Ib)}⁴⁸ and {[(18-C-6)Ag(pyz)]
·X}∞ {X = BF₄⁻ (IIa), CF₃SO₃⁻ (IIb)}⁴⁸ were obtained directly with acceptable yields (see
Supplementary Information). Ia (IIa) and Ib (IIb) just differ from their counterions (Figure
S1). A powder X-ray diffraction (PXRD) analysis was performed to determine the nature of
these Ag(I) CPs. Their powder X-ray diffraction spectra were found to fit nicely with their
homologues simulated from the single-crystal X-ray data described below (Figure 3a). X-ray
photoelectron spectroscopy (XPS) confirmed the +1 oxidation state of Ag in all the four CPs
(Figure 3b). No other elements were detected, except C, N, O, F, B (or S), indicating that their
elemental compositions were in line with their molecular formula. The prepared Ag(I) CPs
were also characterized by IR spectroscopy (Figure S2). Peaks at 1596/1351 cm⁻¹ and
1601/1352 cm⁻¹, were observed for Ia and Ib, respectively, assigned to C=N/C-N stretching
vibrations of the 4,4'-bpy ligands.⁴⁹,⁵⁰ For IIa and IIb, peaks were observed at 1601/1352 cm⁻¹,
corresponding to C=N/C-N stretching vibrations of the pyz ligands.⁵¹ The presence of 18-C-
6 in all Ag(I) CPs was confirmed by observing their typical v(C=O) frequencies {1110 cm⁻¹ (Ia),
1106 cm⁻¹ (Ib), 1111 cm⁻¹ (IIa), and 1106 cm⁻¹ (IIb)}.⁵² Infrared bands at 1051 cm⁻¹ and 1055
cm⁻¹ in Ia and IIa, respectively, confirmed the presence of BF₄⁻ counterions. Finally, the
presence of $CF_3SO_3^-$ in Ib and IIb was confirmed with bands at 1269 cm⁻¹/636 cm⁻¹ and 1268 cm⁻¹/638 cm⁻¹ for SO₃, and 1028 cm⁻¹ and 1032 cm⁻¹ for CF₃, respectively.

## 2.2. Crystal Structure Determination

The crystal structure of the four synthesized Ag(I) CPs was determined by single-crystal X-ray diffraction (Table S1). The structural arrangement shows each silver(I) coordinated to two N atoms of bpy (Ia, Ib) or pyz (IIa, IIb) in a head-to-tail mode, and nested in an 18-C-6 crown ether, leading to an infinite 1D linear structure. The Ag–N bond lengths range from 2.226(13) to 2.308(3) Å (Table S2), with an average bond length of 2.285(5) (Ia), 2.252(13) (Ib), 2.273(3) (IIa), and 2.296(3) (IIb). These bond lengths are similar to those previously reported in Ag-bpy or Ag-pyz coordination compounds.⁴⁴,⁴⁵ The N–Ag–N angles are close to 180° in all the CPs series, with 179.5(2)° for Ia, 175.9(6)~178.4(6)° for Ib, 177.57(15) for IIa, and 174.42(12)~177.96(12)° for IIb. Ag–O (oxygen atoms in 18-C-6) distances for all Ag(I) CPs are in the range of 2.654-2.859 Å (Table S2), comparable to distances usually reported in 18-C-6 silver assemblies, indicating relatively weak interactions between 18-C-6 and silver ions.⁵³⁻⁵⁵

Although the 1D chains in I and II are comparable, they stack in a different manner. Layers of parallel 1D chains stack perpendicularly to each other along the *c* direction in I (Figure 3c and S3), forming pores where the counterions are located (Figure S3). In II, layers of parallel 1D chains are densely packed on top of each other along the *x* direction with the 18-C-6 of one 1D polymer chain inserted in the space formed by two 18-C-6 of two neighboring 1D polymer chains (Figure 3d). These different stackings are indeed important for the photoluminescence properties of these CPs, which will be discussed in the following sections.

## 2.3. Stability Analysis

In general, silver(I) coordination compounds show poor thermal stability, and they usually are sensitive to light and air. Notably, they readily undergo photoreduction to metallic
Ag nanoparticles upon light exposure or transform into Ag₂O following photo-induced ligand dissociation under air condition.⁵⁶⁻⁵⁸ This is not the case here, with the protection of the 18-C-6 macrocycles, the CPs are indeed more inert, giving these polymers excellent stability. The thermal stabilities of the solid Ag(I) CPs were evaluated by thermogravimetric analysis (TGA) (Figure S4). The thermal decomposition process for all CPs includes two steps. In the case of Ia and Ib, the first decomposition starts at 165 °C with mass losses of 45 % and 41 %, close to the theoretically calculated values of 43% and 40%, which are 18-C-6 losses. The second decomposition occurs at 265 °C, releasing 4,4'-benzylpyridine and the counter ion. Similarly, for IIa and IIb, the first decomposition started at 170 °C with mass losses of 14.5% and 13%, close to the theoretically calculated values of 14.8% and 13.5%, corresponding to the loss of pyrazine, while the second decomposition started at 223 °C (IIa) and 211 °C (IIb), associated with the release of 18-C-6 and the counter ion. After these two decomposition steps, the mass percentage of residue was 15.7% in Ia, 20.2% in Ib, and 19.4% in both IIa and IIb, indicating complete decomposition of the organic fraction. Variable temperature X-ray diffraction analysis (Figure S5) further confirmed that these Ag(I) CPs can be kept stable up to nearly 165 °C. Their stability in solution was also evaluated by variable temperature ultraviolet (UV) spectroscopy (Figure S6). Results show that these Ag(I) CPs have a good stability in CH₃CN solutions at 80 °C. These analyses indicate that they show a very good thermal stability compared to other silver(I) coordination compounds.⁴⁴,⁴⁵ In addition, they can be exposed to natural light and air for over one week without showing any decomposition (Figures S7 and S8), indicating that the title Ag(I) CPs series exhibit excellent photo- and air-stabilities.

## 2.4. Excitation Properties

Solid-state UV-vis absorption and UV diffuse-reflectance spectra of the four Ag(I) CPs are shown in Figure S9. They depict similar spectral patterns, with a broad absorption band between 220 and 450 nm. Their optical energy gaps, measured from the solid UV-vis diffuse
reflectance spectra (Figure S9b), are calculated to be 3.11 eV (Ia), 3.06 eV (Ib), 2.92 eV (IIa), and 2.93 eV (IIb), consistent with colorless crystals. The UV-vis absorption spectra (Figure S10a) of I in a CH3CN solution exhibits a prominent peak at ~238 nm ($ε_{max}$ ~238 nm (3.04×10⁴ L·mol⁻¹·cm⁻¹) for Ia, and $ε_{max}$ ~238 nm (1.43×10⁴ L·mol⁻¹·cm⁻¹) for Ib), which is consistent with the absorption peak of 4,4'-bpy ligands. Those of II (Figure S10b) in the same solution show two prominent peaks at ~260 nm ($ε_{max}$ ~260 nm (5.60×10³ L·mol⁻¹·cm⁻¹) for IIa, and $ε_{max}$ ~260 nm (1.43×10⁴ L·mol⁻¹·cm⁻¹) for IIb), and at ~313 nm ($ε_{max}$ ≈313 nm (712.0 L·mol⁻¹·cm⁻¹) for IIa, and $ε_{max}$ ~313 nm (1020.0 L·mol⁻¹·cm⁻¹) for IIb), consistent with absorption peaks of pyz ligands.

The geometrical, electronic and optical properties of the Ag(I) CPs were further investigated by means of density functional theory (DFT) calculations at the PBE0/Def2-TZVP/D3(BJ) level of theory. Calculations were first performed on the oligomeric models [{(18-C-6)Ag}₃(bpy)₄]³⁺ (Ag-bpy-tri) and [{(18-C-6)Ag}₃(pyz)₄]³⁺ (Ag-pyz-tri) used to mimic 1D I and II cationic chains. Their optimized geometries of lowest energy (Figures S11 and S12) were found to be of C₁ symmetry (namely Ag-bpy-tri (C₁) and Ag-pyz-tri (C₁)) and to exhibit non-coplanarity of their ligand rings, in contrast with the crystal structures of I and II in which the ligands are all nearly coplanar (Figure 3). Consequently, calculations were also performed under the C₂ symmetry constraint, which provided the optimized structures Ag-bpy-tri (C₂) and Ag-pyz-tri (C₂) of nearly C₂h symmetry (Figures S11 and S12) in which the ligands can be considered as co-planar. These two structures are less stable than their C₁ counterparts by 0.39 and 0.14 eV, respectively, but their electronic structures are quite similar, as exemplified by the nature and axial properties of their HOMOs and LUMOs plotted for both structures in Figures S11 and S12. As expected, the HOMO in both models and for both C₁ and C₂ geometries is mainly of σ(Ag-bpy/pyz) character, whereas the LUMO is π*(bpy/pyz) in nature (Figures S13 and S14).
For each model, time-dependent DFT (TD-DFT) calculations were performed to simulate the UV-vis spectra of their C₁ and C₂ optimized geometries. The simulated UV-vis spectrum of **Ag-bpy-tri** (C₁) is in a very good agreement with the experimental one recorded for Ia (Figure 4a), with two slightly red-shifted (less than 20 nm) absorption bands. The electronic transitions associated with the simulated optical bands of **Ag-bpy-tri** (C₁) are given in Table S3 and Figure S15. The nature of the electronic transitions, investigated by a natural transition orbital (NTO) analysis, indicate that the band α is mostly due to a strong metal (4d(Ag))–to–ligand (π*(bpy)) charge transfer (MLCT) (Figure 4a,b). The band β involves mixed metal and ligands (4d(Ag), π(18-C-6) and π(bpy)) to π*(bpy) MLCT and ligand–to–ligand charge transfer (LLCT) transitions (Figure 4a,b). In contrast, the two above-discussed bands are more red-shifted in the simulated spectrum of **Ag-bpy-tri** (C₂) (265 and 284 nm). Furthermore, the latter exhibits an experimentally non-observed weak band at 322 nm (Figure 4a), which is mainly attributed to HOMO-7→LUMO and HOMO-8→LUMO+1 transitions (Table S3 and Figure S16). This weak band is also computed around 330 nm in the C₁ structure, but with a very small oscillator strength. This result suggests that in solution compounds I likely lose their ligand coplanarity, the latter being imposed by the crystal forces in the solid. In order to understand the variations of the excitation propeties between I and the individual ligand, the absorption spectrum of bpy was also simulated. The TD-DFT simulated UV-vis spectrum reproduces well the characteristics of the experimental one. The absorption bands α and β are corresponded to HOMO → LUMO and HOMO-2 → LUMO transitions, respectively (Figure S17). Both transitions are of π(bpy) → π*(bpy) nature (Figure S17).

The simulated UV-vis spectrum of **Ag-pyz-tri** (C₁) shows four absorption bands at 469, 342, 268, and 228 nm (Figure 4c). The weak band at 469 nm, describing a HOMO-1 → LUMO transition (Table S4 and Figure S18), which is not observed in the experimental
spectrum of **IIa**, disappears in the simulated spectrum of **Ag-pyz-tri** (*C*₂) (Table S4 and Figure S19), suggesting that, contrarily to compounds **I**, their **II** relatives tend to preserve ligand coplanarity in solution. In order to get a better agreement between the simulated and experimental spectra, calculations on the larger oligomers [{(18-C-6)Ag}₄(pyz)₅]⁴⁺ (**Ag-pyz-tetra**) and [{(18-C-6)Ag}₅(pyz)₆]⁵⁺ (**Ag-pyz-penta**) were carried out under *C*₂ symmetry constraint. One can note that when going from **Ag-pyz-tri** (*C*₂) to **Ag-pyz-penta** (*C*₂) the two absorption bands of higher energy are gradually merging, with a good agreement between the simulated spectrum of **Ag-pyz-penta** (*C*₂) and the experimental spectrum of **IIa** (Figure 4c, Table S4 and Figure S20). A natural transition orbital (NTO) analysis of **Ag-pyz-penta** (*C*₂) indicates that the absorption band α involves both 4d(Ag) → π*(pyz) MLCT and σ(Ag-pyz) → π*(pyz) ligand-centered local excitation (LCLE) (Figure 4c,d). The absorption band β corresponds to a mixed 4d(Ag) and π(18-C-6) to π*(pyz) ligand transitions (Figure 4c,d). In addition, the absorption properties of the individual pyz ligand was also investigated. TD-DFT simulated UV-vis spectrum exhibits a good match with the experimental one, with a minor blue-shifted excitation energies (less than 50 nm). The absorption bands α and β of pyz ligand are associated with HOMO → LUMO and HOMO-1 → LUMO transitions, respectively (Figure S21). Both transitions are of π(pyz) → π*(pyz) nature (Figure S21).

In order to check a potential bias caused by the ligand lone pairs situated at the two ends of the oligomers, we have also simulated the UV-vis spectra of the protonated hypothetical [{(18-C-6)Ag}₃(bpy)₂(bpyH)₂]⁵⁺ and [{(18-C-6)Ag}₅(pyz)₄(pyzH)₂]⁷⁺ species (Figure S22-S25). They exhibit the same shape as those of their **Ag-bpy-tri**(*C*₁) and **Ag-pyz-penta**(*C*₂) homologues and the transitions are of the same nature. Unsurprisingly, they are red-shifted by ~ 100 nm due to the large cationic charge of these species. These results indicate that the largest considered oligomers are reasonably good models for the real polymers **I** and **II**.
**2.5. Photoluminescence Properties**

The PL properties of the Ag(I) CP series were explored at room temperature. Their emissions are very weak in solution, but dramatically enhanced in the solid state. With excitation at 365 nm, **Ia** exhibits intense green emission with a maximum wavelength at 505 nm (Figure S26a). With excitation at 362 nm, **Ib** exhibits intense cyan emission with a maximum at 482 nm (Figure S26b). Excitation of **IIa** at 368 nm results in a cyan emission with a maximum at 525 nm (Figure 5a), whereas that of **IIb** at 366 nm shows a green emission at a maximum of 485 nm (Figure S26c). More importantly, the absolute photoluminescence quantum yield (PLQY) and lifetimes of **I** and **II** are very different from each other in the solid state. The PLQYs and lifetimes measured for **Ia** and **Ib** are comparable (15.3% and 2.28ms, and 14.5% and 13.94 ms, respectively (Figures S27 and S28). Values measured for **II** are much higher (31.2% and 58.28 ms for **IIa**, and 35.8% and 123.54 ms for **IIb**). Among them, the proportion of long-lived components in **IIa** and **IIb** has significantly increased (Table S5). The $K_{nr}$ value (Table S6) of samples **IIa** and **IIb** is significantly lower than that of **Ia** and **Ib**, indicating that their non-radiative decay paths are effectively suppressed, which explains their significantly enhanced PLQYs and lifetimes for the later series originates, in turn, from the higher rigidity of their packing structures (Figure 3c, d). The high QYs, microsecond-scale lifetimes, and large Stokes shifts suggest that the photoemissions of these Ag(I) CPs series are phosphorescent in nature. In addition, these four Ag(I) CPs also exhibit temperature-dependent luminescence behavior. Their PL spectra and lifetime were investigated in the solid state from 97 to 298 K (room temperature), and the **Ia** and **IIa** quantum yields were studied at low temperatures of 77 K. Their color and emission wavelength did not change with temperature variation, but their emission intensities, lifetime and quantum yield (68.1 % and 82.3 %) increase gradually with the decrease of temperature (Figures 5b, S26d-f, S29 and S30). Good correlation between the maximum emission intensity ($I_{max}$) and the temperature (T) were found for the whole Ag(I) CP series (Figure S31), with correlation coefficients of 0.99 (Ia), 0.99 (Ib), 0.99 (IIa), and 0.99 (IIb).

Interestingly, the large difference in the PL properties of compounds **II** between solution and solid state strongly encouraged us to further explore their aggregation induced emission (AIE) activity, which was investigated by controlling the polarity of mixed-solvent systems.

**IIa** was analyzed in a DCM/ether solvent solution, in which the aggregation degree was varied by the volume fraction of ether in the mixed solvent ($f_e = vol_{ether}/vol_{ether+DCM}$).
The dilute solution of **IIa** in DCM was completely non-emissive. A weak green emission was observed when *f*<sub>e</sub> increased to 60%, followed by a further enhancement of the PL intensity with further increasing of the ether fraction. Finally, strong green emission was observed after *f*<sub>e</sub> increased to 90%, indicating the formation of well-dispersed colloids of denser aggregates (Figure 5c). **IIb** displayed similar AIE responses to that of **IIa** in an acetone/ether solvent system, where its emission was triggered when the ether fraction increased to 80% (Figure S32).

Owing to the remarkable phosphorescence properties recorded for both **I** and **II** CPs due to a T₁ → S₀ decay process, the geometric and electronic structures of the T₁ state for the trimer models of **I** (*Ag-bpy-tri* (*C*₁)) and **II** (*Ag-pyz-tri* (*C*₂)) were then investigated using DFT calculations. The optimized T₁ geometry of the first one shows an average Ag–N distance (2.20 Å) slightly shorter than that computed for the S₀ geometry (2.25 Å) (Figure S33). Moreover, the chain structure with T₁ geometry is slightly bent with an angle of 174° between the centered and the two side Ag atoms. The MO diagram of the T₁ state of *Ag-bpy-tri* (*C*₁) is shown on the left side of Figure 6. The resulting electronic structure of the T₁ state involves a slight stabilization of the π*(bpy)-type LUMO and a destabilization of the σ(*Ag-bpy*)-type HOMO, leading to a calculated T₁ → S₀ emission at 495 nm (2.51 eV), in an excellent agreement with the values measured from the PL experiments of **Ia** and **Ib** (505 and 482 nm, respectively). The spin density of the T₁ state of **I** (*Ag-bpy-tri* (*C*₁)) is mainly distributed on the Ag(I) center and its coordinated bpypy ligand, indicating that the triplet excitons are coming from the σ(*Ag-bpy*)-type HOMO (S₀) to the neighboring π*(bpy) type orbitals (Figure S34).

The T₁ geometry of **Ag-pyz-tri** (*C*₂) was optimized in *C*₁ symmetry (not far indeed from *C*₂ symmetry). The optimized average Ag–N distance (2.18 Å) is notably shorter than that in the S₀ geometry (2.30 Å) (Figure S35). In addition, the chain structure of the T₁ geometry is
also slightly bent with an angle of 178.8° between the centered and the two side Ag atoms.

The electronic structure of this T₁ state of **Ag-pyz-tri** (*C*₂) indicates a slight stabilization of the π*(pyz)-type LUMO and a destabilization of the σ(Ag-pyz)-type HOMO (Figure 6a), leading to a calculated T₁ → S₀ emission at 518 nm (2.39 eV) (Figure 6b), which is consistent with the PL emissions measured experimentally for **IIa** and **IIb** (525 and 485 nm, respectively). The spin density of the T₁ state of **II** (**Ag-pyz-tri** (*C*₂)) is mainly distributed on the pyz ligands and to a lesser extent on the Ag(I) centers, indicating that the triplet excitons are transferring from the σ(Ag-pyz)-type HOMO (S₀) to the neighboring π*(pyz) type orbitals (Figure S34).

**2.6. 3D Printing of Ag(I) CPs-Based Luminescent Materials**

With respect to its remarkable emission properties and good solubility, **IIa** was used as a luminescent ink for the production of 3D architectures including the logo letters of Ningxia University (NXU, Figure 5d and 5e), and a UV detector label (Figure 5f and 5g). **IIa** exhibits indeed excellent compatibility with the commercial 3D printing resin which was used. As shown in Figure 5d, the printed letters feature W × H × D about 41.2 mm × 32.8 mm × 4.8 mm with a 1.6 mm × 1.6 mm × 1.6 mm cubic-topological hollow structure. Excitation of these letters with 365 nm UV light results in a bright cyan light at $\lambda_{em}^{max} = 501$ nm (Figure 5e), which is slightly blue-shifted in comparison to that of the **IIa** powder ($\lambda_{em}^{max} = 525$ nm) (Figure S36a). This slight difference is attributed to the interaction of **IIa** with the printing resin.⁵⁹ The printed logo letters display outstanding irradiation stability which can remain luminescent for three months without any quenching. Even under acidic (1 M HNO₃ solution) or alkaline (1 M NaOH solution) conditions (Figures S36b and S36c), the emission intensity of the logo letters did not change within three days. According to the excellent stability of **IIa**, we further produced a UV detector label by dual-color 3D printing technique (Figure 5f and 5g), which could be used as signboard for UV irradiation. The above results strongly
encourage further exploration of Ag(I)-based coordination polymers as stable luminescent
inks in the application field of 3D printing.

**3. Conclusion**

In summary, we have reported here for the first time a crown-ether-directed method to construct luminescent 1D Ag(I) CPs. In their structure, each Ag(I) center is linearly coordinated with bridging bpy or pyz ligands, then nested by an 18-crown-6 (18-C-6) moiety, leading to an infinite “Sugar-coated Haws”-like 1D structure. DFT calculations indicate that the excitation properties of these Ag(I) CPs series originate from a significant metal-to-ligand charge transfer (MLCT) involving the 4d orbitals of the Ag(I) centers and the π* orbitals of the bpy (or pyz) ligands. The remarkable phosphorescence observed in these Ag(I) CPs, which arises from a T₁ → S₀ decay process, is facilitated by the significantly enhanced structural rigidity and suppressed intermolecular interactions between Ag(I) chains. Indeed, this macrocycle-protection-concept is expected to be extended to other Ag(I) CPs systems containing different types of ditopic bridging ligands and macrocycles in future. The AIE behavior observed for CP IIa and IIb holds the promise to employ Ag(I) coordination polymers in various biological applications such as bioimaging. Moreover, we show that CP IIa can successfully be used as a stable luminescent ink component for 3D printing when mixed with a commercial resin. The resulting material maintains excellent irradiation stability for up to three months without any observable luminescence quenching. The present study provides indeed a new avenue for the construction of 1D Ag(I) CPs with exceptional photoluminescence and AIE behavior, opening new horizons for investigating Ag(I) CPs for future functional optical applications.

**Experimental Section**

*Synthesis of {[[(18-C-6)Ag(bpy)]·BF₄}∞ (Ia): AgBF₄ (0.0584 g, 0.3 mmol) was dissolved in CH₃OH (6 mL) solution containing 18-C-6 (0.0793 g, 0.3 mmol) to obtain a colorless*
solution. 4,4'-bpy (0.3 mmol, 0.0468g) was then added under ultrasonication for 10-15 min to obtain a white turbid solution. The reaction mixture was sealed and kept at 70 °C for 20 h. After cooling to room temperature, colorless elongated crystals of Ia were obtained (yield: 12.6% (0.023 g, based on AgBF4)). IR (KBr, cm⁻¹): 2900 (m, nC-H); 1596 (m, nC-N); 1351 (m, nC-N); 1100 (s, nC-O-C); 1051 (s, nB-F).

*Synthesis of ${{{[(18-C-6)Ag(bpy)]·CF₃SO₃}}_∞}$ (Ib): AgCF3SO3 (0.0770 g, 0.3 mmol) was dissolved in CH3OH (6 mL) solution containing 18-C-6 (0.01584 g, 0.6 mmol) to obtain a colorless solution. 4,4'-bpy (0.3 mmol, 0.0468g) was then added under ultrasonication for 10-15 min to obtain a white turbid solution. The reaction mixture was sealed and kept at 70 °C for 20 h. After cooling to room temperature, colorless elongated crystals of Ib were obtained (yield: 32.4% (0.064 g, based on AgOTf)). IR (KBr, cm⁻¹): 2899 (m, nC-H); 1601 (m, nC-N); 1352 (m, nC-N); 1269 (s, nS=O); 1104 (s, nC-O-C); 1028 (s, nC-F), 636 (s, nS-O).

*Synthesis of ${{{[(18-C-6)Ag(pyz)]·BF₄}}_∞}$ (IIa): AgBF4 (0.0584 g, 0.3 mmol) was dissolved in CH3OH (6 mL) solution containing 18-C-6 (0.0793g, 0.3 mmol) to obtain a colorless solution. Pyrazine (0.6 mmol, 0.048g) was then added under ultrasonication for 10-15 min to obtain a white turbid solution. The reaction mixture was sealed and kept at 70 °C for 20 h. After cooling to room temperature, colorless elongated crystals of IIa were obtained (yield: 71.5% (0.1157 g, based on AgBF4)). IR (KBr, cm⁻¹): 2888 (m, nC-H); 1601 (m, nC-N); 1352 (m, nC-N); 1111 (s, nC-O-C); 1054 (s, nB-F).

*Synthesis of ${{{[(18-C-6)Ag(pyz)]·CF₃SO₃}}_∞}$ (IIb): AgCF3SO3 (0.0770 g, 0.3 mmol) was dissolved in CH3OH (6 mL) solution containing 18-C-6 (0.0793 g, 0.3 mmol) to obtain a colorless solution. Pyrazine (0.6 mmol, 0.048g) was then added under ultrasonication for 10-15 min to obtain a white turbid solution. The reaction mixture was sealed and kept at 70 °C for 20 h. After cooling to room temperature, colorless elongated crystals of IIb were obtained (yield: 57.7% (0.103g, based on AgOTf)). IR (KBr, cm⁻¹): 2887 (m, nC-H); 1601 (m, nC-N); 1352 (m, nC-N); 1268 (s, nS=O); 1107 (s, nC-O-C); 1032 (s, nC-F), 638 (s, nS-O).
*Preparation of IIa based printing ink.* Under ultrasonication, crystals of IIa (5 g) were fully dissolved in 25 mL of CH3CN at room temperature. After 10-15 min, the solution was added into 175 g of the light-cured resin (type: FabPro Proto GRY), then alternatively stirred and sonicated for 3 min at room temperature to achieve a uniform ink.

CCDC 2419774 (for **Ia**), CCDC 2419775((for **Ib**), CCDC 2419776(for **IIa**), and CCDC 2419777 (for **IIb**) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

**Acknowledgements**

K.-G. Liu is grateful for financial support from the National Natural Science Foundation of China (Grant No. 92161106) and the Natural Science Foundation of Ningxia (Grant No. 2023AA02004). J. Wei is grateful for financial support from the Natural Science Foundation of Ningxia (Grant No. 2024AAC03032). X. Yang is grateful for financial support from the Key Research and Development Program of Ningxia (Grant No. 2021BEB04066). The authors acknowledge the French Grand Equipment National de Calcul Intensif for HCP support (Project a0010807367). X. Yang and X.-L. Ye contributed equally to this work.

**Conflict of Interests**

The authors declare no conflict of interests.

**Supporting Information**

Supporting Information is available from the Wiley Online Library or from the author.

Received: ((will be filled in by the editorial staff))

Revised: ((will be filled in by the editorial staff))

Published online: ((will be filled in by the editorial staff))
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<figure><img src="image_3.png" /><figcaption>**Figure 1.** Schematic diagram of the (18-C-6)-directed assembly of Ag(I) CPs with enhanced photoluminescence.</figcaption></figure>

<figure><img src="image_4.png" /><figcaption>**Figure 2.** The infinite “Sugar-coated Haws”-like 1D structures of I (a) and II (b). Color code: Ag in pink, C in grey or black, O in red, N in blue; Ag–O interactions in thick two-colored dashed bonds, Ag–N interactions in thick two-colored bonds, C–C and C–N bonds in grey. C–C and C–O bonds in 18-C-6 are highlighted in black (a and b). Counterions and hydrogen atoms are omitted for clarity.</figcaption></figure>
<figure><img src="image_5.png" /><figcaption>**Figure 3.** (a) Powder XRD patterns, (b) XPS full spectra of the four Ag(I) CPs, (c) and (d) stacking structures of CPs I and II, respectively. Color code: Ag in pink, C in grey or black, O in red, N in blue, Ag–O interactions in thick two-colored dashed bonds, Ag–N interactions in thick two-colored bonds, C–C, C–O, and C–N bonds in grey. Counterions and hydrogen atoms are omitted for clarity.</figcaption></figure>
<figure><img src="image_6.png" /><figcaption>**Figure 4.** TD-DFT simulated UV-vis spectra and NTO pairs for different oligomeric models of I (a and b), and II (c and d). The experimental spectra are shown for comparison.</figcaption></figure>

<figure><img src="image_7.png" /><figcaption>**Figure 5.** (a) Room-temperature emission spectra, and (b) temperature-dependent emission spectra of IIa. (c) AIE activities of IIa with different volume ratios of Et₂O in the CH₂Cl₂/Et₂O mixture excited at 368 nm (inset: fluorescence photographs of IIa in CH₂Cl₂ solution with different fractions of Et₂O under UV excitation (365 nm)). (d) Photograph of the light emitting 3D architecture of NXU letters under natural light, and (e) under 365 nm UV light. (f) Photograph of the light emitting warning label under natural light, and (g) under 365 nm UV light.</figcaption></figure>
<figure><img src="image_8.png" /><figcaption>**Figure 6.** (a) Electronic structures of S₀ and T₁ states of **Ag-bpy-tri** and **Ag-pyz-tri**. (b) Simulated phosphorescence emission wavelength of **Ag-bpy-tri** and **Ag-pyz-tri**.</figcaption></figure>
Two series of 18-crown-6-ether directed one-dimensional silver(I) coordination polymers (1D Ag(I)CPs) have been prepared and structurally characterized. Novel and effective strategies were used to prevent intermolecular interactions within each 1D Ag(I)CP, thereby enhancing their photoluminescence at room temperature.

**Keywords:** Silver(I), One Dimensional Coordination Polymer, Photoluminescence, Crown-Ether, aggregations

Xiaojiao Yang,¹# Xiao-Lin Ye,¹# Shu-Han Bao,¹ Dong-Nan Yu,¹ Wenya Jiang,¹ Bintao Wu,¹ Shuaiqi Wang,¹ Kangzhou Wang,¹ Tang Yang,¹ Guozong Yue,² Samia Kahlal,³ Jean-Yves Saillard,³ Jean-François Halet,³ Jianyu Wei,¹ and Kuan-Guan Liu*¹

**Title:** Crown-Ether-Directed Assembly of One-Dimensional Silver(I) Coordination Polymers with Dramatically Enhanced Photoluminescence

<figure><img src="image_9.png" /></figure>

Luminescence

Luminescence

<figure><img src="image_10.png" /></figure>

● = Ag⁺

<figure><img src="image_11.png" /></figure>