Density Functional Theory Study Predicts Low Reorganization Energies for Azadipyrromethene-Based Metal Complexes

Senevirathna, Wasana; Daddario, Cassie M.; Sauvé, Geneviève

doi:10.1021/jz402735c

Cited by 53 publications

(59 citation statements)

References 54 publications

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“…The λint reflects the potential energy changes during the charge transfer process. [25] Usually, λint is defined as:…”

Section: Theoretical Modelsmentioning

confidence: 99%

“…The corresponding position H atoms were replaced by -F or -CN group on the basis of TPB face to face dimer, and the dimers were optimized at ωB97XD/6-31G level. [25] The Heff can be estimated on the basis of the predicted dimers coupling with fragment orbital approach for the neighbor molecular pair. The calculations of Heff were implemented by the PW91PW91/6-31G* [44][45] in the AOMIX program.…”

Section: Computational Detailsmentioning

confidence: 99%

“…[55] ωB97XD functional was used for the corrected evaluation of the energy of weak interaction. [25] These dimers are constructed by using the interlaced parallel manner (as shown in Figure 3) to be the initial geometry. This stacking motif can offer the highest Heff among the dimers of TPB.…”

Section: Dimer Configurationsmentioning

confidence: 99%

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Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

Hu¹,

Yin²,

Chaitanya³

et al. 2016

Croat. Chem. Acta

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Abstract:The electronic structures and charge transport properties of 1,3,5-tripyrrolebenzene (TPB) and its substituted derivatives with -F and -CN groups have been investigated by DFT calculations in combination with the Marcus hopping model. The dimer geometry was optimized by density functional theory method with dispersion force correction being included (DFT-D). Consequently, the charge transfer integral was evaluated. The calculation results show that the introduction of electron-withdrawing substituents does not significantly change the bond lengths and molecular symmetry of TPB, but lower the coplanarity between the pyrrole and benzene rings, especially in the case of CN substitution. Meanwhile, the introduction of electron-withdrawing groups can decrease the energy of the frontier molecular orbital and enhance the air stability. Fluorination makes the λe increase obviously while cyanation dose not. Generally speaking, the λe values of the title compounds are larger than their λh. Except for compounds 6 and 9, all others keep the face to face packing or have a slight slip in dimers, but the center of mass distances increase after fluorination or cyanation due to the distortion of the monomer's coplanarity. The predicted quasi-one-dimensional electron mobility of the dimers is up to 0.433 cm 2 ·V -1 ·s -1 at 298.15 K. The electron injection barriers of 2 and 7 are lower than that of TPB. The TPB derivatives of 1, 2, and 7 are potential n-channel materials with the high electron mobility.

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“…The λint reflects the potential energy changes during the charge transfer process. [25] Usually, λint is defined as:…”

Section: Theoretical Modelsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

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Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

Hu¹,

Yin²,

Chaitanya³

et al. 2016

Croat. Chem. Acta

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“…The addition of pyrrolic phenylacetylene substituents further helped to break the aggregation and to create a favorable nanoscale phase separation in blend films, leading to higher PCEs [9–10]. DFT calculations show that Zn(WS3) 2 is a very large and non-planar molecule with low electron transfer reorganization energy, further supporting its potential to replace fullerenes in OPVs [12]. However, the HOMO and LUMO energy levels of Zn(WS3) 2 in solution are higher than that of the most popular electron acceptor phenyl-C 61 -butyric acid methyl ester (PCBM, Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

Etheridge¹,

Fernando²,

Pejić³

et al. 2016

Beilstein J. Org. Chem.

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SummaryHomoleptic zinc(II) complexes of di(phenylacetylene)azadipyrromethene (e.g., Zn(WS3)2) are potential non-fullerene electron acceptors for organic photovoltaics. To tune their properties, fluorination of Zn(WS3)2 at various positions was investigated. Three fluorinated azadipyrromethene-based ligands were synthesized with fluorine at the para-position of the proximal and distal phenyl groups, and at the pyrrolic phenylacetylene moieties. Additionally, a CF3 moiety was added to the pyrrolic phenyl positions to study the effects of a stronger electron withdrawing unit at that position. The four ligands were chelated with zinc(II) and BF2 + and the optical and electrochemical properties were studied. Fluorination had little effect on the optical properties of both the zinc(II) and BF2 + complexes, with λmax in solution around 755 nm and 785 nm, and high molar absorptivities of 100 × 103 M−1cm−1 and 50 × 103 M−1cm−1, respectively. Fluorination of Zn(WS3)2 raised the oxidation potentials by 0.04 V to 0.10 V, and the reduction potentials by 0.01 V to 0.10 V, depending on the position and type of substitution. The largest change was observed for fluorine substitution at the proximal phenyl groups and CF3 substitution at the pyrrolic phenylacetylene moieties. The later complexes are expected to be stronger electron acceptors than Zn(WS3)2, and may enable charge transfer from other conjugated polymer donors that have lower energy levels than poly(3-hexylthiophene) (P3HT).

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“…1) that have drawn considerably more attention in recent years because they possess high molar absorptivities near 300 and 600 nm. [29][30][31] However, the azadipyrromethenes ligands have not been explored as the N^N ancillary ligand in neutral heteroleptic Ir(III) complexes to date. 25,26 Unique photophysical properties have rendered them, and are widely applied in biological systems, organic electronic devices and solar energy conversion.…”

Section: Introductionmentioning

confidence: 99%

Unveiling photophysical properties of cyclometalated iridium(iii) complexes with azadipyrromethene and dipyrromethene ancillary: a theoretical perspective

Ren

Shan

et al. 2014

RSC Adv.

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A density functional theory/time-depended density functional theory was used to investigate a series of heteroleptic Ir(III) complexes (1-4) employing azadipyrromethene and closely related dipyrromethene derivatives as N^N ancillary ligands, in an effort to explore the underlying reasons of non-radiative behaviour of 1 and further adjust the photophysical properties by the modification of N^N ancillary ligands. The results reveal that the non-emissive phenomenon of 1 can be attributed to the weak 3 ILCT character of the emissive excited state and large structure distortion, as well as the small T opt 1 -S opt 0 energy gap. Upon tailoring the N^N ancillary ligands, the geometry distortion of 2-4 becomes obviously smaller in comparison with 1, accordingly, the spectrum properties are also markedly affected.For instance, the enlargement of frontier molecular orbital energy gaps from 1 to 4 results in the blueshift of their absorption and emission spectra, which is considered to be dominated by the ancillary ligand, while there is a little contribution from the Ir(III) center. Importantly, further analysis on the quantum yield (F PL ) of these complexes also indicates a vital role of N^N ancillary ligands. It is intriguing to note that the designed complex 4 without pendant phenyl rings substituent in the ancillary ligand, possesses an efficient indirect spin-orbital coupling route, larger transition electric dipole moment (m S3 ), higher T opt 1 -S opt 0 energy gap and smaller S 3 -T 1 splitting energy (DE (S3-T1) ), which ensure its higher F PL compared to other complexes. Electronic supplementary information (ESI) available: Tables (S1) Optimized geometrical parameters for 1 in the ground state at different functional levels with experimental data. (S2) Calculated absorption spectra of 1 in CHCl 3 media with different functionals. (S3) Variations of geometry parameters from S 0 to T 1 state for 1-4. (S4) Calculated intramolecular centroid-centroid distances for 1-3. (S5) Molecular orbital compositions (%) of 1-4 in the ground state. (S6) Calculated singlet excited states in detail for 1-4. (S7-S8) The 5d(Ir) orbital compositions (%) in the T 1 state and the electronic transition of S n states based on the T 1 geometries of 2-4. (S9) The net spin values located on Ir(III) of 3 MLCT and 3 MC states for 1-4. (S10) Cartesian coordinates of 1 at the S 0 and T 1 optimized geometry. Fig. (S1) The synthetic routes of the designed ancillary ligands L1-L3. (S2) Optimized structures of 1-4 in the ground state. (S3) Orbital interaction diagram for 1. (S4) Calculated spin-density distributions for the 3 MC states. (S5) Energy level diagram of 3 MLCT/pp* and 3 MC excited states for 1-4 with the normalized S 0 levels. See

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Density Functional Theory Study Predicts Low Reorganization Energies for Azadipyrromethene-Based Metal Complexes

Cited by 53 publications

References 54 publications

Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

Unveiling photophysical properties of cyclometalated iridium(iii) complexes with azadipyrromethene and dipyrromethene ancillary: a theoretical perspective

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