DOI: 10.5281/zenodo.15266985
title: Data and Code Related to the Article: Improving Triplet-Triplet Annihilation Upconversion Output by a Triplet Mediator Approach: Mechanistic Insights on Homo and Hetero-Annihilation in Three Component Systems

description: Matlab code for modelling and construction Figures: 4d, 4e, 4f, 5a, 5c, 6 and 7

MatlabCode.zip contains 6 matlab script (.m) files, and 8 matlad data files (.mat).

7 of the data files contain the raw data from flash-photolysis experiments as described by the file name. The data is stored in the variable 'Data' containing data from various experimental time windows. Each 'Data' cell contains columns with time and delta absorption values. Further details of the flash-photolysis setup can be found in the ESI of the main article.

The 8th data files containts the UC emission intensity at different excitation intensities. Here columns 1-2 are excitation intensity and emission intensity for a sample with 4CzBN and 1mM TIPSNap , columns 3-4 for a sample with 4CzBN and 0.01mM Nap and 1 mMBT, and columns 5-6 for a sample with 4CzBN and 0.1mM Nap and 1 mM BT and columns 7-8 for a sample with 4CzBN and  1 mM BT.

The main script is main_mediatorUC.m. Rate constants, concentrations and excitation power density can be changed as desired. The main script reads the data files and performs a fit to the mediator and annihilator flash-photolysis data, using the functions in mediatorFit.m and annihilatorFit.m, respectively.

The other files, RateMediator.m , Steadystate.m and Steadystate_enhancedTET.m contain functions for the rate equations describing the kinetics of the system. The two latter files are written in steady-state form and the former in differential equation form. These are called within the main script and solved to yield steady-state or time-dependent concentrations, respectively.

Raw data for Figure 5b - time resolved upconversion emission spectra

File Fig5b.zip contains 18 text files of upconverted emission spectra at time points from 0.75 microseconds to 200 microseconds. Time and experimental settings are found in the file name, e.g. Sample concentration, excitation power (2mJ) and wavelength (410 nm), cuvette geometry 10x4 mm, gain for CCD camera (255V), time after excitation (0.75-200 microseconds), gate width (gw, 30 ns) and number of averaged spectra (32). Spectra in Figure 5b have been area normalized and residual emission from 4CzBN has been removed for early time points.

Raw data for ns-TA spectra, Figure 4a-c

Files Fig4a/b/c.zip contains text files with the nanosceond transient absorption spectra recorded at specific time points as per figure 4 a-c in the main manuscript. Time and experimental settings are found in the file name, e.g. Sample concentration, excitation power (2mJ) and wavelength (410 nm), cuvette geometry 10x10 mm, gain for CCD camera (160V), time after excitation (100 ns-150 us), gate width (gw, 10 ns) and number of averaged spectra (8).

Raw data for Figure 2a – 0.01 mM Nap emission, 0.01 mM BT emission and BT absorption

File Figure 2a.zip contains three excel files for 0.01 mM Nap emission, 0.01 mM BT emission and BT absorption respectively. File with BT absorption consists of molar absorptivity e (M-1cm-1) and that with 0.01 mM Nap emission and 0.01 mM BT emission consist of emission intensity normalized at the value corresponding to the maximum molar absorptivity value of BT.

Raw data for Figure 2b – 0.01 mM Nap emission, Nap absorption and 1 mM Nap emission

File Figure 2b.zip contains three excel files for 0.01 mM Nap emission, Nap absorption and 1 mM Nap emission respectively. File with Nap absorption consists of molar absorptivity e (M-1cm-1) and that with 0.01 mM Nap emission and 1 mM Nap emission consist of emission intensity normalized at the value corresponding to the maximum molar absorptivity value of Nap.

Raw data for Figure 3a – A vertical column graph of TTA–UC QY (%) vs concentration of annihilator Nap (mM) with error bar

File Figure 3a.zip contains a single excel file with TTA-UC QY (%) for systems with sensitizer 4CzBN (25 µM) and annihilator Nap at three different concentrations (0.01 mM, 0.1 mM and 1 mM) in the presence and absence of mediator. In the excel file, column A consists of concentration of annihilator Nap (mM). Column B consists UC QY (%) for 1 mM BT with Nap concentration 0.01 mM and 0.1 mM and the corresponding error bar in the column C. Column D is UC QY (%) for Nap of concentration 0.01 mM, 0.1 mM and 1 mM respectively and the corresponding error bar in column E. Column F consists UC QY (%) with 10 mM BT and 0.1 mM Nap and the corresponding error bar in column G.

Raw data for Figure 3b – TTA-UC emission spectra for the different systems consisting of sensitizer 4CzBN, annihilator Nap in the presence or absence of mediator BT

File Figure 3b.zip contains  a single excel file with the data for TTA-UC emission spectra for the UC system consisting of 0.1 mM Nap + 1 mM BT + 25 µM 4CzBN, 1 mM Nap + 25 µM 4CzBN, 0.01 mM Nap + 1 mM BT + 25 µM 4CzBN and 1 mM BT + 25 µM 4CzBN respectively. 

Raw data for Figure 3c – Plot of integrated upconversion emission intensity as a function of power density

File Figure 3b.zip contains  three excel files with the data for the plot of TTA-UC integrated emission intensity vs Power density (W/cm2) for the TTA-UC system 0.1 mM Nap + 1 mM BT + 25 µM 4CzBN, 1 mM Nap + 25 µM 4CzBN and 0.01 mM Nap + 1 mM BT + 25 µM 4CzBN respectively. 

Raw data for Figure S1-S7 – Plot of integrated upconversion emission intensity as a function of power density for annihilator Nap, with/ without mediator BT, and sensitizer 4CzBN TTA-UC system 

File Figure S1-S7.zip contains  seven excel files with the data for the plot of TTA-UC integrated emission intensity vs Power density (W/cm2) for the system annihilator Nap, with/ without mediator BT, and sensitizer 4CzBN and for mediator BT and sensitizer 4CzBN. Figure S1: 25 µM 4CzBN + 1 mM Nap, Figure S2: 25 µM 4CzBN + 0.1 mM Nap + 1 mM BT, Figure S3: 25 µM 4CzBN + 0.1 mM Nap, Figure S4: 25 µM 4CzBN + 0.01 mM Nap + 1 mM BT, Figure S5: 25 µM 4CzBN + 0.01 mM Nap, Figure S6: 25 µM 4CzBN + 1 mM BT and Figure S7: 25 µM 4CzBN + 0.1 mM Nap + 1 mM Ph.

Raw data for Figure S8-S13 – Plot of UV-vis absorption spectra for the TTA-UC system consisting of annihilator Nap, with/ without mediator BT, and sensitizer 4CzBN TTA-UC system before and after laser excitation in the experiment for the determination of Ith value 

File Figure S1-S7.zip contains  six excel files with the data for the plot of UV-vis absorption spectra for the TTA-UC system. Figure S8: 25 µM 4CzBN + 0.1 mM Nap + 1 mM BT, Figure S9: 25 µM 4CzBN + 0.1 mM Nap, Figure S10: 25 µM 4CzBN + 0.01 mM Nap + 1 mM BT, Figure S11: 25 µM 4CzBN + 0.01 mM Nap, Figure S12: 25 µM 4CzBN + 1 mM BT and Figure S13: 25 µM 4CzBN + 0.1 mM Nap + 1 mM Ph.

Raw data for Figure S14-S15 – Plot of UV-vis absorption spectra for the TTA-UC system consisting of annihilator Nap, with mediator BT, and sensitizer 4CzBN

File Figure S14-S15.zip contains  two excel files with the data for the plot of UV-vis absorption spectra for the TTA-UC system. Figure S14 has data for 25 µM 4CzBN + 1 mM Nap, 25 µM 4CzBN + 1 mM BT and 25 µM 4CzBN + 0.01 mM Nap + 1 mM BT.

Figure S15 has data for 25 µM 4CzBN + 1 mM Nap, 25 µM 4CzBN + 1 mM BT, 25 µM 4CzBN + 0.01 mM Nap + 1 mM BT and 25 µM 4CzBN + 0.01 mM Nap + 1 mM Ph.

Raw data for Figure S16-S21 – Plot of integrated upconversion emission intensity as a function of power density for annihilator PPE-A, with/ without mediator DPA, and sensitizer PtOEP TTA-UC system 

File Figure S16-S21.zip contains  six excel files with the data for the plot of TTA-UC integrated emission intensity vs Power density (W/cm2) for the system annihilator PPE-A, with/ without mediator DPA, and sensitizer PtOEP and for mediator DPA and sensitizer PtOEP. 

Figure S16: 15 µM PtOEP + 0.01 mM PPE-A + 0.1 mM DPA, Figure S17: 15 µM PtOEP + 0.01 mM PPE-A, Figure S18: 15 µM PtOEP + 0.001 mM PPE-A + 0.1 mM DPA, Figure S19: 15 µM PtOEP + 0.001 mM PPE-A, Figure S20: 15 µM PtOEP + 0.01 mM PPE-A + 1 mM DPA, Figure S21: 15 µM PtOEP + 0.1 mM DPA.

Raw data for Figure S22-S27 – Plot of  UV-vis absorption spectra for the TTA-UC system consisting of annihilator PPE-A, with/ without mediator DPA, and sensitizer PtOEP TTA-UC system before and after laser excitation in the experiment for the determination of Ith value

File Figure S22-S27.zip contains  six excel files with the data for the plot of UV-vis absorption spectra for the TTA-UC system before and after laser excitation in the experiment for the determination of Ith value. 

Figure S22: 15 µM PtOEP + 0.01 mM PPE-A + 0.1 mM DPA, Figure S23: 15 µM PtOEP + 0.01 mM PPE-A, Figure S24: 15 µM PtOEP + 0.001 mM PPE-A + 0.1 mM DPA, Figure S25: 15 µM PtOEP + 0.001 mM PPE-A, Figure S26: 15 µM PtOEP + 0.01 mM PPE-A + 1 mM DPA and Figure S26: 15 µM PtOEP + 0.1 mM DPA.

Raw data for Figure S28 – Plot of UV-vis absorption and emission spectra of BT and Nap for the emission quantum yield determination of BT

File Figure S28.zip contains  four excel files. File name is in accordance with the SI Figure S28 of main manuscript. 

Figure S28_bottom left – UV-vis absorption of Nap (1 µM, 2 mM, 3 µM, 4 µM and 5 µM respectively).

Figure S28_bottom right – Emission spectra of BT (1 µM, 2 mM, 3 µM, 4 µM and 5 µM respectively).

Figure S28_top left – UV-vis absorption of BT (1 µM, 2 mM, 3 µM, 4 µM and 5 µM respectively).

Figure S28_top right – Emission spectra of Nap (1 µM, 2 mM, 3 µM, 4 µM and 5 µM respectively).

Raw data for Figure S29 – Plot of integrated flourescence intesnity vs absorbance

File Figure S29.zip contains  two excel files. File name is in accordance with the SI Figure S29 of main manuscript, plot of integrated flourescence intesnity vs absorbance (Figure S29_left for Nap and Figure S29_right for BT)

Raw data for Figure S30 – Stern-Volmer plot

File Figure S30.zip contains  one excel file. File name is in accordance with the SI Figure S30 of main manuscript. It consist of data for Stern-Volmer plot for Nap and BT.

Raw data for Figure S31 – Decay trace of 4CzBN emission on quenching with Nap or BT 

File Figure S31.zip contains two excel files. One for the quenching of 4CzBN emission with different concentration of Nap (Figure S31 left) and other for the quenching of 4CzBN emission with different concentration of BT (Figure S31 right).

Raw data for Figure S32-S42 

File Figure S32-S42.zip consist of eleven excel files. Excel file name is in accordance with the SI of main manuscript.

Raw data for Figure  S43-S58 – NMR data 

File Figure S32-S42.zip consist of sixteen MNova files which includes both 1H-NMR and 13C-NMR. MNova file name is in accordance with the SI Figure S32-S42 of main manuscript.