Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization

Chakraborty, Saptarshi; Kar, Haridas; Sikder, Amrita; Ghosh, Suhrit

doi:10.1039/c6sc02640k

Cited by 32 publications

(13 citation statements)

References 61 publications

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“…The temperature-dependent variations correspond to the J-type π–π stacking aggregation. The degree of aggregation (α agg ) as a function of temperature depicts a sigmoidal trend, which fits the isodesmic chain growth model of supramolecular polymerization ( R 2 = 0.996) . Some thermodynamic parameters could then be deduced from this model.…”

Section: Results and Discussionsupporting

confidence: 52%

“…The degree of aggregation (α agg ) as a function of temperature depicts a sigmoidal trend, which fits the isodesmic chain growth model of supramolecular polymerization (R 2 = 0.996). 30 Some thermodynamic parameters could then be deduced from this model. The enthalpy release (ΔH iso ) during the chain elongation is −1088.9 kJ mol −1 , along with the equilibrium constant (K iso = 2.94 × 10 4 M −1 ) at the melting temperature (T m = 315.0 K).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Ultrathin Supramolecular Architectures Self-Assembled from a C₃-Symmetric Synthon for Selective Metal Binding

Cheng

Zhang

et al. 2020

ACS Appl. Mater. Interfaces

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Ultrathin supramolecular nanoarchitectures are an emerging class of two-dimensional (2D) materials with dynamic features that facilitate their on-demand functions. However, facile and efficient synthesis for multiple 2D topologies by taking advantage of spontaneous self-assembly is limited. In this work, we report the synthesis of ultrathin supramolecular nanoarchitectures from the self-assembly of a π-conjugated C 3-symmetric synthon (tribenzyloxybenzoic acid, TBBA), with the benzene-1,3,5-tricarboxamide core terminated by three carboxylic acids. Supported by the carboxylic acid–amide hydrogen-bonding and π–π/CH−π interactions, TBBA self-assembles into freestanding microsheets with the thickness of around 2 nm, demonstrating considerable integrity in different solvent systems or in the presence of carboxylic acid binders such as bipyridines. The deprotonation of the carboxylic acids endows TBBA with amphiphilicity, allowing for the formation of mixed micelles that are sensitive to transition-metal ions. Selectively, TBBA3– shows relatively strong coordination to Cu(II), giving rise to long and thin organometallic ribbons (about 3 nm thickness) with a pronounced aging process. Kinetically insufficient coordination was probed by various characterization techniques and molecular dynamics simulation, which played a vital role in directing the formation of thin ribbons. This work provides a proof-of-concept study for a feasible and versatile construction of both flexible and rigid 2D supramolecular nanostructures with promising applications.

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Section: Results and Discussionsupporting

confidence: 52%

Section: ■ Results and Discussionmentioning

confidence: 99%

Ultrathin Supramolecular Architectures Self-Assembled from a C₃-Symmetric Synthon for Selective Metal Binding

Cheng

Zhang

et al. 2020

ACS Appl. Mater. Interfaces

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“…As the size of the side‐chain substituent increases from methyl in F1⋅Q to ethyl in F13⋅Q, the arrangement changes from Class 1 to Class 3. Mixed stacking is found to be favored with increasing size of elements (S in F7⋅Q and F9⋅Q, Se in F10⋅Q, and Te in F11⋅Q) and the length of the side chain substituted on F (F7⋅Q, F9⋅Q, F10⋅Q, and F11⋅Q) and Q (in F⋅Q2), which sheds light on the role of steric hindrance in directing the nature of packing in the studied Fx⋅Q and F⋅Qy co‐crystals. However, the nearly planar non‐steric F8 also forms a Class 2 co‐crystal with Q (F8⋅Q), perhaps because of the higher interaction between the nearly flat electron‐delocalized F derivative with the acceptor Q.…”

Section: Resultsmentioning

confidence: 99%

“…As the size of the side-chain substituent increases from methyl in F1·Q to ethyl in F13·Q, the arrangement changes from Class 1t oC lass 3. Mixed stacking is found to be favored with increasing size of elements (S in F7·Q and F9·Q, Se in F10·Q, and Te in F11·Q) and the length of the side chain substituted on F( F7·Q, F9·Q, F10·Q, and F11·Q) and Q( in F·Q2), which sheds light on the role of steric hindrance [82][83][84] in direct- Pendas' interacting quantum atoms (IQA) approach [55] was employed to further characterize the nature of the S···S interactions and comprehendt heir significance in directingt he cofacial stacking and sidewise parallel-displaced arrangement of D-D in Class 1a nd Class 2s ystems. IQA analysis was performed on 1) F6-F6 and F6a-F6a sidewise parallel-displaced dimers that exhibitedS ···S interactions ( Figure S5 a,b, Supporting Information), 2) the F6-F6 co-facial dimer that indicated C···S interactions ( Figure S5 c, Supporting Information), and 3) the F3·Q trimer that exhibited S···S interactions (FigureS5d,S upporting Information).…”

Section: Classmentioning

confidence: 85%

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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“…If R > 1, homointeractions are more favored; if R < 1, heterointeractions are favored. In the former case of self-sorted homopolymers where R approaches infinity, the monomers can distinguish between self and nonself in the system. , In the latter case of alternating copolymers where R < 1, the introduction of strong heterointeractions, such as charge transfer interactions and electrostatic interactions, between monomers gives perfectly alternating supramolecular copolymers. − However, most cases are often not under these extreme, yet simple, conditions. ,− Therefore, it is important to unravel the complexity and predict the microstructures of supramolecular copolymer systems.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Complexity of Supramolecular Copolymerization Dictated by Triazine–Benzene Interactions

Jansen

Schnitzer

et al. 2021

J. Am. Chem. Soc.

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Supramolecular copolymers formed by the noncovalent synthesis of multiple components expand the complexity of functional molecular systems. However, varying the composition and microstructure of copolymers through tuning the interactions between building blocks remains a challenge. Here, we report a remarkable discovery of the temperature-dependent supramolecular copolymerization of the two chiral monomers 4,4′,4″-(1,3,5triazine-2,4,6-triyl)tribenzamide (S-T) and 4,4′,4″-(benzene-1,3,5-triyl)tribenzamide (S-B). We first demonstrate in the homopolymerization of the two individual monomers that a subtle change from the central triazine to benzene in the chemical structure of the monomers significantly affects the properties of the resulting homopolymers in solution. Homopolymers formed by S-T exhibit enhanced stability in comparison to S-B. More importantly, through a combination of spectroscopic analysis and theoretical simulation, we reveal the complex process of copolymerization: S-T aggregates into homopolymers at elevated temperature, and upon slow cooling S-B gradually intercalates into the copolymers, to finally give copolymers with almost 80% alternating bonds at 10 °C. The formation of the predominantly alternating copolymers is plausibly contributed by preferred heterointeractions between triazine and benzene cores in S-T and S-B, respectively, at lower temperatures. Overall, this work unravels the complexity of a supramolecular copolymerization process where an intermediate heterointeraction (higher than one homointeraction and lower than the other homointeraction) presents and proposes a general method to elucidate the microstructures of copolymers responsive to temperature changes.

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Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization

Cited by 32 publications

References 61 publications

Ultrathin Supramolecular Architectures Self-Assembled from a C₃-Symmetric Synthon for Selective Metal Binding

Ultrathin Supramolecular Architectures Self-Assembled from a C₃-Symmetric Synthon for Selective Metal Binding

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

Unraveling the Complexity of Supramolecular Copolymerization Dictated by Triazine–Benzene Interactions

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Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization

Cited by 32 publications

References 61 publications

Ultrathin Supramolecular Architectures Self-Assembled from a C3-Symmetric Synthon for Selective Metal Binding

Ultrathin Supramolecular Architectures Self-Assembled from a C3-Symmetric Synthon for Selective Metal Binding

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

Unraveling the Complexity of Supramolecular Copolymerization Dictated by Triazine–Benzene Interactions

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Ultrathin Supramolecular Architectures Self-Assembled from a C₃-Symmetric Synthon for Selective Metal Binding

Ultrathin Supramolecular Architectures Self-Assembled from a C₃-Symmetric Synthon for Selective Metal Binding