Hydrogen Bonding Versus π-Stacking in Charge-Transfer Co-crystals

Yee, Nathan; Dadvand, Afshin; Hamzehpoor, Ehsan; Perepichka, Dmitrii F.

doi:10.1021/acs.cgd.1c00309

Cited by 17 publications

(15 citation statements)

References 34 publications

(66 reference statements)

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“…Getmanenko, Risko, and co-workers reported theoretical evidence for ambipolar mobility along edge-to-edge contacts in 7,7,8,8-tetracyanoquinodimethane (TCNQ) and dithieno[3,2-a:2′,3′-c]phenazine (DTPhz) . The interplay of hydrogen bonding and π–π stacking interactions influences charge transfer in small organic cocrystals exhibiting ambipolar charge transport . Naphthalene- and thiazole-based molecular systems have been exploited as potential materials in the field of organic electronics and act as lead compounds in the development of pharmaceutical drugs. − Our ongoing interest in probing the origin of supramolecular structural motifs with emergent properties − employing weak interactions motivated us to design novel naphthothiazole , derivatives.…”

Section: Introductionmentioning

confidence: 99%

Resonance-Assisted Hydrogen Bonding and π–π Stacking Modulates the Charge Transfer Coupling in Crystalline Naphthothiazoles

John

Narayanasamy

Sudhakaran

et al. 2022

Crystal Growth & Design

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Supramolecular chemistry employs noncovalent interactions to coax π-conjugated molecules into ordered functional assemblies. Herein, we report 5-methoxynaphtho[1,2-d]thiazol-2-amine (NTN) and 4-bromo-5-methoxynaphtho[1,2-d]thiazol-2-amine (NTNB) assembled into π-stacked columns integrated by lateral resonance-assisted hydrogen bonds (RAHBs) orthogonal to the π–π stacking direction. Quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) analyses were utilized to characterize the presence and stability of intermolecular RAHBs in NTN and NTNB. In contrast to the parallel packing of NTN, bromine substitution promoted antiparallel packing in NTNB with noticeable π–π stacking and orbital overlap favoring efficient charge transfer coupling (V e/h). Antiparallel stacking in NTNB exhibits a dipole moment minimization and aromaticity gain. The relevance of aromaticity in stabilizing π–π stacked systems is highlighted by the aromaticity gain in antiparallel stacked dimers of NTNB and can be extended to estimate the nature and strength of noncovalent interactions. Crystal packing plays a crucial role in regulating the charge transport properties, as can be observed from higher electron and hole transfer coupling along the π–π stacked and RAHB dimer, respectively, in NTN. However, in NTNB maximum electron and hole transfer coupling occurs selectively along the π–π stacked antiparallel dimer. The anisotropic mobility plots from a combination of first-principles quantum chemical calculations and the Marcus–Hush formalism confirm that both RAHB and π–π stacked dimers contribute to the mobility in NTN, but NTNB exclusively benefits from the π–π stacked dimer. Modulating noncovalent interactions for charge carrier transport can harness the innate potential of organic molecules to engineer novel optoelectronic materials.

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Section: Introductionmentioning

confidence: 99%

Resonance-Assisted Hydrogen Bonding and π–π Stacking Modulates the Charge Transfer Coupling in Crystalline Naphthothiazoles

John

Narayanasamy

Sudhakaran

et al. 2022

Crystal Growth & Design

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Section: Structure–property Relations Of Ctcsmentioning

confidence: 99%

“…In two structurally similar mixed stacking CTCs, although 2a contains a stronger electron D compared with 1a, the E g and degree of charge transfer of 2a are both significantly lower than that of 1a because 2a has only π–π interactions but no hydrogen bond interactions. Therefore, they considered that hydrogen bonds can enhance the electronic interaction and impart charge transport properties to the cocrystals compared to only π‐stacking CTCs (Figure 1a) [ 36 ] In addition, the ionicity of the components and the electronic structure of the conductive columns of CTCs are regulated by hydrogen bonds. For example, the hydrogen bonds can modulate the molecular arrangement and enhance the redox ability of the CTCs fashioned by TTF‐imidazoles and p ‐chloranil, creating an organic metal.…”

Section: Structure–property Relations Of Ctcsmentioning

confidence: 99%

Organic Charge‐Transfer Complexes for Near‐Infrared‐Triggered Photothermal Materials

Zheng

et al. 2022

Small Structures

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When light-absorbing materials are excited by visible or near-infrared (NIR) light, they will eventually come back to their original equilibrium state, and a part of the absorbed photon energy is released as heat through nonradiative transitions during this process. The heat is determined by absorption ability under excitation wavelength and photothermal conversion efficiency, which is strongly related to the radiative and nonradiative transition rates. A good photothermal material should have high photothermal conversion efficiency, suitable absorption spectrum, and high light absorption ability, and can be used for photoacoustic imaging, [1][2][3] cancer photothermal therapy, [4,5] seawater desalination, [6][7][8] lightdriven thermoelectric system, [9,10] and so on. Especially, the second infrared window (NIR-II, 1000-1700 nm) absorbed photothermal materials have received much attention in biological applications for weak light scattering, low tissue absorption, deep tissue penetration depth, and high maximum permission exposure (up to 1.0 W cm À2 under 1064 nm laser excitation). Up to now, varied photothermal materials can roughly be categorized into two parts: inorganic materials and organic counterparts. For the potential long-term toxicity of inorganic materials, organic counterparts possess low toxicity, easy structural modification, tunable properties, and abundant molecules, so organic photothermal materials have rapidly developed during the last two decades. Typical organic photothermal materials embrace porphyrin, [11] cyanine dyes, [12,13] diketopyrrolopyrrole, [5] polyaniline, [14] polypyrrole, [15] semiconducting polymers, charge-transfer complexes (CTCs), [16] and so on.Among them, the CTCs are composed of electron-donating (D) and electron-accepting (A) molecules, and formed once charge delocalization takes place between the D and A leading to an enhanced molecular polarization, [17] which can be described as [18] In 1973, a famous CTC (TTF-TCNQ) was first reported, which was made of tetrathiafulvalene and 7,7 0 ,8,8 0 -tetracyanoquinodimethane; the researchers found that the electrical conductivity of TTF-TCNQ was comparable with metals. [19] From then on, the electrical properties of CTCs have got much attraction,

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“…[10][11][12][13][14] Consequently, the ability to design supramolecular architectures based on directional assembly of carbon-based systems remains an unsolved fundamental problem of crystal engineering. [15][16][17] Over the past two decades, halogen bonding has emerged as a versatile directional interaction in the crystalline solid state, offering access to a wider range of acceptor atoms than commonly seen for hydrogen bonding. [18][19][20][21][22][23][24][25][26][27][28] Notably, scattered structural reports show that halogen bonds can form between electron-deficient iodine atoms as donors and flat, electronrich π-systems, such as anilines, as acceptors.…”

Section: Introductionmentioning

confidence: 99%

Halogen Bonding to Carbon: a Directional Interaction for the Reliable Design of Supramolecular Architectures Based on Non-derivatized Aromatic Carbon Systems

Vainauskas

Borchers

Arhangelskis

et al. 2023

Preprint

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Carbon, although the central element in organic chemistry has been traditionally neglected as a target for directional supramolecular interactions. The design of supramolecular structures involving carbon-rich molecules, such as arenes, has almost exclusively been limited to π-stacking of aromatic systems, or derivatization with heteroatoms as sites for molecular recognition. Here, we demonstrate that C-I···Cπ halogen bonds to carbon-based π-systems can be reliably used as direction-al interactions for the creation of extended structures based on planar, as well as curved aromatic systems, without any need for derivatization or π-stacking. Specifically, we describe the first systematic study of a series of cocrystals containing non-derivatized carbon-only aromatic systems of different sizes and shapes, including polycyclic aromatic hydrocarbons (PAHs) and fullerene C60, which are held together by directional halogen bonds to aromatic carbon atoms. In a large majority (~90%) of structures, the C-I···Cπ halogen bonding with PAHs leads to a supramolecular ladder-like motif, in which the PAHs act as the rungs and halogen bond donors as rails, demonstrating this motif as the first example of a supramolecular synthon based on carbon. These results, supported by novel cocrystal structures, theoretical calculations, and a systematic analysis of the Cambridge Structural Database, offer a new, previously overlooked paradigm for the assembly of carbon-only aromatic systems, not based on π-stacking, but via specific, directional halogen bonding. This new ability to use a car-bon-based supramolecular synthon to direct the assembly aromatic systems provides an exciting opportunity to create materials with new and modified properties based on non-derivatized aromatic systems, as seen from large red and blue shifts in solid-state luminescence for cocrystals of pyrene, coronene and perylene, as well as the appearance of room-temperature phosphorescence upon cocrystal formation.

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Hydrogen Bonding Versus π-Stacking in Charge-Transfer Co-crystals

Cited by 17 publications

References 34 publications

Resonance-Assisted Hydrogen Bonding and π–π Stacking Modulates the Charge Transfer Coupling in Crystalline Naphthothiazoles

Resonance-Assisted Hydrogen Bonding and π–π Stacking Modulates the Charge Transfer Coupling in Crystalline Naphthothiazoles

Organic Charge‐Transfer Complexes for Near‐Infrared‐Triggered Photothermal Materials

Halogen Bonding to Carbon: a Directional Interaction for the Reliable Design of Supramolecular Architectures Based on Non-derivatized Aromatic Carbon Systems

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