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Timestamp: 2019-04-23 13:58:01+00:00

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Entropy is one of the fundamental quantities which links emerging research areas like flexibility and defect engineering in inorganic–organic hybrid materials. Additionally, a delicate balance between entropy and enthalpy can lead to intriguing temperature-driven transitions in such materials. Here, we briefly overview traditional material design principles, highlight the role of entropy in the past and discuss how computational methods can help us to understand and quantify entropic effects in inorganic–organic hybrid materials in the future.
Keith T. Butler is Research Associate in the Department of Chemistry at the University of Bath. He received his BA in medicinal chemistry from Trinity College Dublin and PhD in computational chemistry at University College London. Following postdoctoral research at the University of Sheffield on silicon solar cells, he joined the UK SUPERSOLAR project at Bath to focus on new materials for solar energy conversion and the physical chemistry of porous solids.
Aron Walsh is Professor of Theory in the Centre for Sustainable Chemical Technologies at the University of Bath. He received his BA and PhD in chemistry from Trinity College Dublin, and subsequently held positions at the National Renewable Energy Laboratory and University College London. In 2015 he was awarded the EU-40 prize from the European MRS for his work on hybrid inorganic–organic solar cells. His research focuses on the theory and simulation of functional materials including electroactive metal-organic frameworks.
Tony Cheetham is the Goldsmiths’ Professor of Materials Science at the University of Cambridge and the Treasurer and Vice President of the Royal Society. He has received numerous awards for his work in materials chemistry, including the Somiya Award of the IUMRS (2004), the Platinum Medal of the IOM3 (2011), and a Chemical Pioneer Award from the American Institute of Chemists (2014). He is a member of the German National Academy of Sciences (Leopoldina) and the American Academy of Arts and Sciences, and holds honorary doctorates from Versailles (2006), St. Andrews (2011), Tumkur (2011) and Warwick (2015).
Gregor Kieslich is an inorganic chemist focusing on crystal chemistry and structure–property relations in functional solids and hybrid frameworks. He studied chemistry between 2006 and 2010 at the Johannes Gutenberg University in Mainz. After completing his PhD in 2013 with Prof. W. Tremel, he moved to Cambridge University to work with Prof A. K. Cheetham. Throughout his career he has been awarded several fellowships, including the Konrad-Adenauer PhD fellowship and the DFG research fellowship. In August 2016 he will take on his new role as Junior Research Leader, under the mentorship of Prof. R. A. Fischer at the Technical University of Munich.
Since the beginning of modern crystal chemistry, the ultimate goal of materials science has been the design of materials with distinct physical properties. In this pursuit, many intriguing materials and systems with complex stimuli-signal behaviour have been prepared.1–3 For instance, Kitagawa et al. reported on the gas separation of CO2 and H2C2 by using (inverse) sorption selectivity in metal–organic frameworks,4 and Lotsch et al. described the preparation of layered systems in which the photonic properties vary upon changes in humidity.5 The complexity of the underlying structure–property-relationships, however, makes the targeted design of materials with specific properties challenging. This becomes even more complex for composite systems where the properties of two different materials are interconnected with each other.
Taking one step back and looking at more fundamental guidelines, some early milestone were the works by Goldschmidt,6 Pauling7 and Baur.8 In their studies, they approached the question ‘under which circumstances a certain crystal structure forms’ and established the first important guidelines in crystal chemistry. Factors such as packing density, coordination numbers and connectivity of polyhedra were identified. Together with the Hard and Soft Acid and Bases (HSAB) theory of Pearson,9 as well as sources of tabulated data, such as the Shannon ionic radii,10 solid state chemists possess a powerful tool-kit. These concepts can then be used to predict the existence and properties of many materials, and moreover, how properties can be altered in existing compounds. A simple and topical example is the decreasing band-gap of [CH3NH3]PbX3 along the halide series X = Cl−, Br− and I−.11 The decreasing electronegativity of the halide anion leads to an increased band dispersion and therefore to a smaller band-gap. More examples of various materials can be found in the elaborate works by Hoffman,12 Goodenough13 and Whangbo14 amongst others.
The entropy of a perfect crystal is zero at 0 K. For inorganic materials, engineering entropy is closely related to defect chemistry and site disorder.24 The minimum in Gibbs free energy of a system is determined by a delicate balance between enthalpy and entropy at finite temperatures, this drives the formation of intrinsic defects. Such defects, more precisely their concentration, can be used to alter properties such as the ionic conductivity in solid state electrolytes, e.g. CaO or Y2O3 stabilised ZrO2.25 A further intriguing example is the defect chemistry of Fe1−xO at temperatures above 540 °C where specific defect cluster have been found, e.g. four Fe2+ defect sites surrounding a tetrahedral Fe3+.26 Here entropy leads to the formation of defects at high temperatures, whereas cluster formation is driven to enhance coulombic interactions. Site disorder, for example in alloys, is a source for configurational entropy and oftentimes challenging to assess. A stunning example in which disorder is paired with defect chemistry is Cu2−xSe.27 In this compound, Se atoms form a rigid face-centred cubic lattice, whereas copper ions are highly disordered with liquid-like mobilities.
All these effects together lead to a shallow energy surface in hybrid materials and accentuate the effect of usually weaker interactions, such as ligand field stabilisation energy, substituents of organic linkers and so on. The possibility of amorphisation and recrystallization of metal–organic frameworks is in strong agreement with this observation.51,52 It also seems that entropy is a basic principle for emerging research areas of flexibility and defects in hybrid materials. Many application-relevant properties are closely related to entropic effects, such as sorption properties in porous frameworks and temperature driven phase transitions, as well as the responses to external pressures for sensing applications, defect-driven carrier concentrations and mobilities, and thermal conductivities. Similar conclusions can be drawn for the field of porous organic cages.53,54 Despite the difficulties attendant with the estimation and computation of entropic effects, the task of understanding them is important enough to warrant serious research and further development in this area. Moreover, the growing availability of computational power means that the techniques for studying the effects of entropy can now be applied routinely to a wide range of hybrid systems.
As alluded to above, entropy in the solid-state can be broadly separated into three classes: (i) vibrational entropy, (ii) rotational entropy and (iii) configurational entropy. For metallic systems electronic entropy can also play an important role, but we restrict our discussion to materials with an electronic band gap. The theoretical basis for describing these effects in solid-state systems has been known for well over half a century. Starting from the harmonic oscillator model of a solid developed by Debye55 and Einstein,56 the lattice dynamics approach, formulated by Born,57 provides the necessary apparatus for the quantitative calculation of vibrations (phonon modes) and the vibrational contributions to crystal stability. Rotational effects on the other hand are almost absent in solely inorganic materials, where structural units, usually ions or atoms, are rotationally invariant. In hybrid materials, where molecules constitute an element of the structure, rotations become possible and can be accounted for through statistical mechanical approaches. Finally, in multi-component materials – for example double perovskites,58,59 mixed tetrahedral semiconductors or lattices with defect sites – disorder of site occupancy introduces the possibility of configurational entropy.
with kB the Boltzmann constant, h the Planck constant, T the absolute temperature and ω(q,s) the phonon frequencies. The expense of the calculations arises from the fact that populating the Hessian requires many calculations to determine the forces on each ion. Additionally, it is necessary to use supercell expansions of the unit cell in order to ensure that all non-negligible elements of the Hessian are accounted for. The Hessian can be obtained in real space (finite displacement) or reciprocal space (perturbation theory). Most electronic structure packages provide the functionality to calculate the dynamical matrix. Additionally, several excellent post-processing packages have recently been developed,60–62 to obtain phonon spectra and interesting thermal properties, such as lattice expansion and thermal conductivity.
Lattice dynamics calculations also offer a powerful tool to simulate theoretical Raman and infra-red (IR) vibrational spectra of materials.69–73 Recently, the spectrum of the hybrid framework [CH3NH3]PbI3 has been calculated and compared to experimental data to allow for improved characterisation.74 Although the crystal vibrational contributions are expensive to calculate, more and more examples emerge that highlight the important nature of such effects, particularly in hybrid materials that exhibit soft phonon modes. These phonon modes emerge from weak interactions such as hydrogen bonds and are thermally accessible.
Molecular dynamics, MD, provides another route to exploring vibrational effects and has been used to demonstrate the impact of vibrational entropy in determining phase changes in organic polymer crystals.34 A recent study obtained the vibrational entropy of a radical magnetic molecular crystal as the difference between the internal energy of the system – obtained from MD simulations in canonical ensemble – and the Helmholtz free energy of the system – obtained by thermodynamic integration. This methodology is costly, as MD requires many thousands of steps to obtain well equilibrated quantities, whilst thermodynamic integration requires many (typically tens to hundreds) individual MD runs; however, in return one obtains quantities which transcend the (quasi-)harmonic approximation made in lattice dynamics techniques.
In hybrid systems an understanding of configurational order/disorder relationships is critical in a number of scenarios. By mixing cations in MOFs it is possible to tune magnetic,83 catalytic84 and dynamic85 properties. In lead-based hybrid halide perovskites with the general formula APbX3 (A = [CH3NH3]+ or [NH2CHNH2]+ and X = Br− or I−), some of the best efficiency solar cells are now obtained by mixing of organic cations on the A-site and halides on the X site.86 Recently DFT calculations have shown the complexity of the Br/I solid solution [CH3NH3]PbI1−xBrx, which demonstrates the spinodal decomposition of a mixed halide solution into iodide and bromide rich phases at room temperature.87 Engineering defects in MOFs is another area of growing importance and there has been a flurry of interest in harnessing the effects of defects to tune materials properties.47,48,88 For example, in HKUST-1 with careful linker selection, properties such as porosity and band-gap can be gradually tuned and computationally rationalised.89 Although this area is only starting to emerge, the importance of configurational entropy cannot be overestimated. In all of these systems, the configurational entropy will be key in driving systems between correlated and un-correlated impurity/defect centres, as such calculations are expected to play a crucial role in the design of hybrid solid-solutions and defects.
where Ij are the principle moments of inertia of the molecule and σ is the symmetry number. In soft-matter simulations, however, rotational entropic effects have been shown to play important roles in phenomena such as water confinement in carbon nanotubes90 and protein–ligand interactions.91 Methods have been proposed for partitioning total entropy from molecular dynamics simulations to obtain a rotational contribution.92 Rotational disorder is also a key consideration in the study of “plastic crystals”, where molecular orientations are determined stochastically at finite temperatures. In plastic crystals a number of useful concepts have been developed for understanding the effects of rotational disorder, for example molecular pseudospins, which describe the orientation of a molecule in space, and rotator functions, which are functions that change continually with varying orientation.93 It is our strong feeling that in the field of hybrid materials the study of rotational entropic effects is an area of growing importance. For instance, rotationally driven order–disorder transitions lead to marked changes in dielectric properties.2 From the computational side, however, this is little understood and represents one of the future directions of this field, and much can be learned from the simulation of soft-matter systems (Table 1).
In spite of the progress to date, there are outstanding challenges in the areas of computational materials science, which must be addressed in order to capture all phenomena and to facilitate a truly predictive computational design of hybrid materials.
Vibrational entropy: going beyond the quasi-harmonic approximation. The current state-of-the-art in accounting for vibrational entropy from lattice dynamic calculations is the quasi-harmonic approximation. Thermal expansion is treated as a series of volume-dependent harmonic calculations. This neglects anharmonicity in the energy surface which can become important at higher temperature, as recently demonstrated for defect formation in Al and Cu.94 Higher-order anharmonic effects are essential for describing systems that exhibit displacive or order–disorder instabilities.
Configurational entropy: disorder of multi-component systems. The challenge here is largely implementational. Most tools developed for considering the effects of site disorder in materials deal with single atomic or ionic units. For hybrid systems it becomes necessary to consider disorder of molecular units, too; in this case a unit at a particular crystal site can change its effect by changing its orientation. These extra orientational degrees of freedom increase the combinatorial space to be considered, but will be important for obtaining quantitative values for hybrid systems. We note that methods developed for inorganic systems have been applied to molecular crystals38,39 and extensions to hybrid materials should not be arduous.
A final important development in the area of computation, which we have not mentioned previously, is the application of high-throughput automated calculations and statistical (or machine) learning. Although phonon calculations are significantly more expensive than standard total energy calculations, high-throughput studies are beginning to be reported.101 The first libraries of computed phonon data are now available102 and facilitate the application of machine learning techniques. In any machine learning study the availability of good descriptors, simple properties which can be related to more complex outcomes of the systems, is critical.103 One factor suggested by Greer is the discrepancy in ion sizes in a multi-ternary system.104 A recent data-mining study drawing on empirical data105 suggested two descriptors – Ω and δ – the former based on entropy of mixing, the latter based on radii to predict high-entropy alloy formation. Another study, derived from calculated data, proposes a descriptor based on “thermodynamic density of competing crystalline states” to predict the formation of bulk metallic glasses.106 We have no doubt that data-mining techniques will become ever more important in the design of materials and the elucidation of the role of entropy.
Undoubtedly, entropy has a tremendous impact on the crystal chemistry of hybrid inorganic–organic materials and includes all aspects of dynamic effects and structure–property relationships. Recent breakthroughs in the field have combined chemical design principles, experimental observations and computational chemistry with each other.107,108 From that viewpoint it is clear that only a common effort involving different research areas, and therefore research groups, is capable of fully unravelling the power of entropy as a design principle in the future.
In the majority of cases where entropy is considered in solid-state systems, only one of the three types we have outlined is considered. Examples exist, however, such as the defect dependent NTE in UIO-66,109 where a combination of configurational disorder together with vibrational entropy account for the material's properties. The first step towards an elaborate understanding of entropy is the analysis of each contribution and its importance within the system as a whole. A recent example where combined efforts lead to a deep understanding is the solar cell material [CH3NH3]PbI3. At a first glance, the system seems to be rather simple, but [CH3NH3]PbI3 has proven to exhibit a highly dynamic inorganic framework.110,111 In these hybrid perovskite systems, more specifically their alloys, the important roles of both configurational87 and vibrational74 entropy have been emphasised by computational studies. Such studies provide important guidelines and methodological blueprints for future investigations into structure–property relationships in hybrid metal–organic systems.
In hybrid materials in general, it is well established that long organic linkers and porous materials lead to high vibrational entropies, while, at the same time, substitutional defects seem to be relatively easy to introduce in hybrid materials. For the impact of rotational entropy, the field of hybrid materials can learn from related research areas. For instance, the structure of helical polymers is mainly influenced by salt-bridge like interactions which have been designed accordingly.112 It is worth remembering here that the nearly unlimited variety of organic linker materials allow for the specific design of hydrogen bonds, van der Waals forces, π–π interactions and so on.
Ideally, computational chemistry approaches for hybrid systems will become as sophisticated as presently available methods for inorganic and soft-matter materials. As mentioned earlier, there are many aspects that need to be tackled in the future; however, experimental scientists are now creating a need for such theories. This can lead to fast and fruitful progress, as has been recently shown in the area of gas-sorption in metal–organic frameworks. The enormous interest in the materials science community, including within industry, has led to a need for computational models to describe such phenomena. As a consequence, computational codes were modified and guided the synthesis of new highly-porous gas-storage materials, aided by the use of high-throughput screening techniques.113–115 It is our belief that a similar demand for insight will lead to developments in the understanding of entropy in hybrid inorganic–organic materials.
In conclusion, we have discussed the role of structural and chemical disorder in the context of hybrid materials chemistry. We have outlined three primary contributions to entropy in metal–organic systems and have given examples of how these are related to current developments in the field of hybrid inorganic–organic materials. In particular, focus has been laid on the developments and key challenges in the field of computational chemistry.
50 years after R. H. Fowler stated that “[t]here is no hope for a logical definition of absolute entropy”,116 referring to the endless possible sources of entropy, significant progress has been made in enumerating and understanding the important sources of entropy and helped to understand experimental findings. Thus we believe that the progress made can be used to understand and engineer the physical and chemical properties in hybrid inorganic–organic materials in the future. It will be exciting to see if in the future a combined approach of computational chemistry, experimental approaches and chemical design principles can help to ‘find’ the philosopher's stone of materials science – the targeted design of materials with distinct physical properties.
The work at Bath has been supported by the European Research Council (Grant no. 277757) and the EPSRC (Grant no. EP/M009580/1 and EP/J017361/1). GK thanks the Deutsche Forschungsgemeinschaft, DFG, for financial support (KI1870). GK and AKC gratefully thanks the Ras Al Khamiah Center for Advanced Materials for financial support. GK thanks Prof Roland A. Fischer for inspiring discussions.
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