Crystalline triphenylamine substituted arenes: solid state packing and luminescence properties

Mallia, Ajith R.; Niyas, M. A.; Hariharan, Mahesh

doi:10.1039/c6ce02321e

Cited by 28 publications

(14 citation statements)

References 53 publications

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“…To better understand the mechanochromic performance of TPA‐AN crystal, its single‐crystal data were obtained and analyzed. The crystal of TPA‐AN belongs to a monoclinic crystal system and crystallizes in the space group C2/c, which agrees on the recent report, but differ from the structure reported by Yang and co‐workers . Each unit cell contains four molecules and the detailed information is included in Table S1 (Supporting Information).…”

Section: Resultssupporting

confidence: 85%

“…As illustrated in Figure c, two main interactions exist between adjacent TPA‐AN molecules: (1) the hydrogen atom to the large π‐conjugation central benzene ring (CH•••π), and (2) the hydrogen atom on benzene rings to the lone pair electrons of N atom of TPA (CH•••N weak hydrogen bond). It is worth mentioning that the CH•••N and CH•••π interactions play key roles in the single‐crystal cultivation . Additionally, there are no interactions between the anthracene parts, which is distinct from many widely reported anthracene‐substituted materials with the π–π stacking .…”

Section: Resultsmentioning

confidence: 94%

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Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State

et al. 2017

Advanced Optical Materials

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4‐(Anthracen‐9‐yl)‐N,N‐diphenylaniline (TPA‐AN) is a typical molecule belonging to a donor–acceptor system. Here, the ordered crystal and the powder of TPA‐AN are used for high‐pressure Raman and fluorescence experiments, and their spectroscopic features under the shearing force of grinding and the hydrostatic pressure applied by a diamond anvil cell (DAC) are compared. The mechanochromism of TPA‐AN is discussed in detail based on the analysis of its single‐crystal structure and pressure‐driven spectral changes. During the DAC compression process, the TPA‐AN crystal shows an obvious emission band shift (from 476 to 600 nm) along with a new intramolecular charge transfer state that is separated from the hybridized local and charge transfer excited state and extremely sensitive to external force. Once the pressure is relieved, the Raman and fluorescence spectra both entirely self‐recover without a secondary force. To the authors' knowledge, TPA‐AN crystal is one of the largest emission shift organic mechanochromic fluorescent materials among reported publications. The reversible mechanochromic property of TPA‐AN for a wide‐range emission shift implies a great application potential as smart stimuli‐responsive layer in the fields of sensing, organic light‐emitting diode displays, and data storage.

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Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 94%

Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State

et al. 2017

Advanced Optical Materials

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“…The Cambridge Structural Database (CSD) provides an excellent platform for a comprehensive study of a series of F⋅Q derivatives crystallized over around half a century. Our continued interests in devising de novo strategies to modulate crystal structure to enhance the functional properties of materials led to a comprehensive database study on F⋅Q‐based co‐crystals. In the current study, crystal structures of F⋅Q derivatives identified from CSD were critically analyzed with the aim of introducing a general classification of multicomponent D‐A crystals based on their packing modes.…”

Section: Introductionmentioning

confidence: 99%

“…Ac ombined study based on as eries of F·Q-based co-crystals to address the subtle intermoleculari nteractions that dictate the crystalline packinga nd its corresponding structure-packing-property relationship remains elusive. The Cambridge StructuralD atabase (CSD) [44] provides an excellent platform for ac omprehensive study of as eries of F·Q derivatives crystallized over aroundh alf ac entury.O ur continued interests in devising de novo strategies to modulate crystal structure to enhance the functional properties of materials [45][46][47][48][49][50][51] led to ac omprehensive database study on F·Q-based co-crystals. In the current study,c rystal structures of F·Q derivatives identified from CSD were critically analyzed with the aim of introducing ag eneral classification of multicomponent D-A crystalsb ased on their packing modes.…”

Section: Introductionmentioning

confidence: 99%

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Niyas

Vijay

Hariharan

2018

Chemistry A European J

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Among the various donor-acceptor (D-A) charge-transfer co-crystals investigated in the past few decades, tetrathiafulvalene-tetracyanoquinodimethane (F⋅Q, popularly known as TTF⋅TCNQ)-based co-crystals have fascinated materials chemists owing to their exceptional conducting and magnetic properties that arise from the packing in crystal structures. Here, crystallographic information files of eighteen F⋅Q-based co-crystals are extracted from the Cambridge Structural Database (CSD) and classified into Class 1 (D-on-D and A-on-A segregated stacks; F⋅Q, F1⋅Q-F6⋅Q, and F⋅Q1), Class 2 (-A-D-A-D-A-D- mixed stacks; F6a⋅Q-F11⋅Q and F⋅Q2), and Class 3 [-A-D-A-A-D-A-; Class 3a (F12⋅Q and F13⋅Q) and -D-D-A-A-; Class 3b (F14⋅Q)] systems according to their packing modes. Hirshfeld surface analysis, PIXEL energy calculations, and quantum theory of atoms in molecules (QTAIM) analysis are performed on the selected multicomponent charge-transfer crystals for the first time, in an attempt to explore the driving forces that give rise to different classes of 3 D crystal packing, which in turn mandates the expedient electronic properties exhibited by the investigated co-crystals. PIXEL calculations reveal that the dispersion energy component makes the maximum contribution to the total lattice energy for most of the F⋅Q-based co-crystals under study. Although the Q-on-Q dimer is the energetically most favored dimer in F⋅Q, the substituents on F capable of forming hydrogen-bonding, C⋅⋅⋅S, and other weak intermolecular interactions result in the greater stability of the F-on-F dimer for F1⋅Q-F6⋅Q (except F2⋅Q). The C⋅⋅⋅S, C ⋅⋅⋅S, S⋅⋅⋅N, and π⋅⋅⋅π interaction-driven D-on-A dimer is found to be the most stable dimer of all the Class 2 co-crystals. Band structure and density-of-state calculations of the representative co-crystals in each class indicate different electronic structures according to the packing arrangement. F⋅Q and F6⋅Q with a high interaction of electronic orbitals between D-on-D and A-on-A in segregated stacks are found to be metal-like (bandgap, E =0.003 eV) and metallic (overlapping bands in the Fermi level), respectively, whereas the polymorph of F6⋅Q belonging to Class 2 (F6a⋅Q) displays a semiconductor-type band structure (E =0.053 eV). F12⋅Q of Class 3a exhibits a metal-like band structure (E =0.001 eV). The fine tuning of chromophores with diverse functional substituents capable of triggering weak intermolecular interactions that give rise to the desired packing and charge-transfer properties has the potential to open floodgates of opportunity for research in the chemistry of materials and fabrication of efficient electronic devices.

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“…[10][11][12][13][14][15] The propeller-shaped triphenylamine (TPA) core has gained immense interestf or HTMs in OLEDs, owing to good thermal stability,a high glass transition temperature, and efficient hole-transporting ability coupled with low ionisation potential. [8,[16][17][18][19][20] Functionalisationo ft he TPAm olecule would result in diverse crystallinep acking arrangements, [21] which, in turn, couldf ine-tune the optoelectronic properties of the core TPAm oiety by enhancing the p-p interorbital interaction between phenyl rings. [9] Thus, at horough understandingo ft he interconnection betweent he molecular structure, packing arrangementa nd transport properties is indispensable in designing efficient and economical organic materialst hat are pertinent for optoelectronicd evices.…”

Section: Introductionmentioning

confidence: 99%

Deciphering the Multifarious Charge‐Transport Behaviour of Crystalline Propeller‐Shaped Triphenylamine Analogues

Ambili

Sasikumar

Hridya

et al. 2019

Chemistry A European J

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A collection of para‐substituted propeller‐shaped triphenylamine (TPA) derivatives have been computationally investigated for charge‐transport characteristics exhibited by the derivatives by using the Marcus–Hush formalism. The various substituents chosen herein, with features that range from electron withdrawing to electron donating in nature, play a key role in defining the reorganisation energy and electronic coupling properties of the TPA derivatives. The TPA moiety is expected to possess weak electronic coupling on the basis of poor orbital overlap upon aggregation, owing to the restriction imposed by the propeller shape of the TPA core. However, the substituent groups attached to the TPA core can significantly dictate the crystal‐packing motif of the TPA derivatives, wherein the variety of noncovalent intermolecular interactions subsequently generated drive the packing arrangement and influence electronic coupling between the neighbouring orbitals. Intermolecular interactions in the crystalline architecture of TPA derivatives were probed by using Hirshfeld and quantum theory of atoms‐in‐molecules techniques. Furthermore, symmetry‐adapted perturbation theory analysis of the TPA analogues has revealed that a periodic arrangement of energetically stable dimers with significant electronic coupling is essential to contribute high charge‐carrier mobility to the overall crystal.

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Crystalline triphenylamine substituted arenes: solid state packing and luminescence properties

Cited by 28 publications

References 53 publications

Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State

Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Deciphering the Multifarious Charge‐Transport Behaviour of Crystalline Propeller‐Shaped Triphenylamine Analogues

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