Novel Shape‐Memory Polymer Based on Hydrogen Bonding

Summary: Due to a large difference in storage modulus below and above the glass transition temperature, a novel shape‐memory poly[(methyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)]/poly(ethylene glycol) semi‐interpenetrating polymer networks structure was synthesized, which is stabilized by hydrogen‐bonding interactions. The recovery ratio of these polymers could reach 99%. In such a system the maximum molecular weight of PEG required for the semi‐IPNs formation reaches 1 000.

Transition from the temporary shape (chem) to the permanent shape (four rods) for a shape‐memory P(MMA‐co‐VP)/PEG1000 semi‐IPNs.     

Protonation Switching to the Least‐Basic Heteroatom of Carbamate through Cationic Hydrogen Bonding Promotes the Formation of Isocyanate Cations

We found that phenethylcarbamates that bear ortho‐salicylate as an ether group (carbamoyl salicylates) dramatically accelerate O?C bond dissociation in strong acid to facilitate generation of isocyanate cation (N‐protonated isocyanates), which undergo subsequent intramolecular aromatic electrophilic cyclization to give dihydroisoquinolones. To generate isocyanate cations from carbamates in acidic media as electrophiles for aromatic substitution, protonation at the ether oxygen, the least basic heteroatom, is essential to promote C?O bond cleavage. However, the carbonyl oxygen of carbamates, the most basic site, is protonated exclusively in strong acids. We found that the protonation site can be shifted to an alternative basic atom by linking methyl salicylate to the ether oxygen of carbamate. The methyl ester oxygen ortho to the phenolic (ether) oxygen of salicylate is as basic as the carbamate carbonyl oxygen, and we found that monoprotonation at the methyl ester oxygen in strong acid resulted in the formation of an intramolecular cationic hydrogen bond (>C?O⁺?H???O<) with the phenolic ether oxygen. This facilitates O?C bond dissociation of phenethylcarbamates, thereby promoting isocyanate cation formation. In contrast, superacid‐mediated diprotonation at the methyl ester oxygen of the salicylate and the carbonyl oxygen of the carbamate afforded a rather stable dication, which did not readily undergo C?O bond dissociation. This is an unprecedented and unknown case in which the monocation has greater reactivity than the dication.     

Acid‐Induced Shift of Intramolecular Hydrogen Bonding Responsible for Excited‐State Intramolecular Proton Transfer

The significant progress recently achieved in designing smart acid‐responsive materials based on intramolecular charge transfer inspired us to utilize excited‐state intramolecular proton transfer (ESIPT) for developing a turn‐on acid‐responsive fluorescent system with an exceedingly large Stokes shift. Two ESIPT‐active fluorophores, 2‐(2‐hydroxyphenyl)pyridine (HPP) and 2‐(2‐hydroxyphenyl)benzothiazole (HBT), were fused into a novel dye (HBT‐HPP) fluorescent only in the protonated state. Moreover, we also synthesized three structurally relevant control compounds to compare their steady‐state fluorescence spectra and optimized geometric structures in neutral and acidic media. The results suggest that the fluorescence turn‐on was caused by the acid‐induced shift of the ESIPT‐responsible intramolecular hydrogen bond from the HPP to HBT moiety. This work presents a systematic comparison of the emission efficiencies and basicity of HBT and HPP for the first time, thereby utilizing their differences to construct an acid‐responsive smart organic fluorescent material. As a practical application, red fluorescent letters can be written using the acid as an ink on polymer film.     

Host–Guest Hydrogen Bonding Varies the Charge‐State Behavior of Magnetic Sponges

The electron‐donor(D) and ‐acceptor(A)‐assembled D₂A‐layer framework [{Ru₂(m‐FPhCO₂)₄}₂TCNQ(OMe)₂]?nDCE ( 1‐nDCE ; m‐FPhCO₂^?=m‐fluorobenzoate; TCNQ(OMe)₂=2,5‐dimethoxyl‐7,7,8,8‐tetracyanoquinodimethane; DCE=1,2‐dichloroethane) undergoes drastic charge‐ordered state variations via three distinct states that are a two‐electron‐transferred state (2e‐I), a charge‐disproportionated state (1.5e‐I), and a one‐electron‐transferred state (1e‐I), depending on the degree of solvation by nDCE. The pristine form 1‐4DCE has a paramagnetic 2e‐I state, which eventually produces the solvent‐free form 1 in 1.5e‐I via an intermediate state 1‐nDCE (n≤1) in 1e‐I. Resolvation of 1 stabilizes 1‐DCE , allowing it to switch between 1.5e‐I and 1e‐I, and to become ferrimagnetic with a T_c of 30 K (1.5e‐I) and 88 K (1e‐I). The stabilization of the 1e‐I state of 1‐DCE is due to the presence of host–guest hydrogen bonding that enables to suppress the electron‐donation ability of D even in an identical framework with 1 .     

4-硝基-1,3-丁二烯基胺分子的氢键效应

在从头计算的水平上, 利用杂化密度泛函理论研究了溶剂对4-硝基-1,3-丁二烯基胺分子的几何结构、分子内的电荷分布和电荷转移态的能量漂移的影响. 在四种极性溶剂中, 我们构造了包括氢键作用的超分子结构. 分别研究了由极化连续模型模拟的溶剂和溶质分子的长程相互作用, 溶剂和溶质分子的氢键作用, 以及溶剂和溶质分子的整体作用对分子结构和性质的影响. 研究结果表明氢键作用引起了溶质分子结构和性质的较大变化, 从而将明显地影响该类分子的非线性光学性质. 因此, 在模拟溶剂效应时需要考虑氢键作用.     

Tautomerization‐Mediated Molecular Switching Between Six‐ and Seven‐Membered Rings Stabilized by Hydrogen Bonding

1,3,4,6‐Tetraketones typically undergo keto–enol tautomerism forming bis‐enols stabilized by intramolecular hydrogen bonding in two six‐membered rings. However, 1,3,4,6‐tetraketones derived from the terpene ketone camphor and norcamphor exist as isomers with two distinguishable modes of intramolecular hydrogen bonding, namely, the formation of six‐ or seven‐membered rings. The structural requirements for this so far unknown behavior were investigated in detail by synthesis and comparison of structural analogues. Both isomers of such 1,3,4,6‐tetraketones were fully characterized in solution and in the solid state. Intriguingly, they slowly interconvert in solution by means of tautomerism–rotation cascades, as was corroborated by DFT calculations. The influence of temperature and complexation with the transition metals Pd, Rh, and Ir on the interconversion process was investigated.     

Eutectic Molecular Liquids Based on Hydrogen Bonding and π–π Interaction for Exfoliating Two‐dimensional Materials and Recycling Polymers

Eutectic molecular liquids (EMLs) based on hydrogen‐bonding interaction and π–π stacking were prepared. We found that the thermodynamic properties like initial decomposition temperature and glass transition temperature of EMLs are mainly dominated by the hydrogen bond donor, which is beneficial for designing and preparing new EMLs. These new liquid systems could be applied in the field of environmental and material science.     

A Helicate‐Based Three‐State Molecular Switch

The control of structural transformations triggered by external signals is important for the development of novel functional devices. In the present study, it is demonstrated that helicates can be designed to structurally respond to the presence of different counterions and to adopt either a compressed or an expanded structure. Reversible switching is not only possible between those two states, furthermore, the twist of the aggregate also can be controlled. Thus, three out of four possible states of a helicate (expanded/left‐handed, expanded/right‐handed, compressed/left‐handed) based on an enantiomerically pure ester bridged dicatecholate ligand are specifically addressed by introduction, exchange, or removal of countercations. This approach is used to reversibly switch between the different states or to successively address them.     

Theoretical Study on Hydrogen Bonding of Mono‐ and Dihydrated Complexes of 7‐(3′‐Pyridyl)indole in Excited States

The intermolecular hydrogen bonds of mono‐ and dihydrated complexes of 7‐(3′‐Pyridyl)indole (7‐3′PI) have been investigated using the time‐dependent density functional theory (TD‐DFT) method. The electrostatic potential analysis of monomer 7‐3′PI and 7‐(3′‐Pyridyl)indole‐water (7‐3′PI‐W) indicates that an intermolecular hydrogen bond between two waters can be formed for 7‐(3′‐Pyridyl)indole‐2water (7‐3′PI‐2W) complex. The calculated bond lengths of the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W in the S₁ state (the first excited singlet state) are all shortened compared to the ground state. By the analysis of bond length, charge population and infrared spectra, it is demonstrated that the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W are all strengthened upon electronic excitation to the S1 state. Moreover, the fluorescence of 7‐3′PI‐W and 7‐3′PI‐2W are all red‐shifted to larger wavelength compared to monomer 7‐3′PI. The red‐shift of fluorescence peak of 7‐3′PI‐W and 7‐3′PI‐2W should be attributed to the change of hydrogen bond interaction before and after photoexcitation. Therefore, it can be concluded that the intermolecular hydrogen bonding strengthening in the excited S₁ state induces the fluorescence weakening of 7‐3′PI.     

Complementary Hydrogen Bonding Modulates Electronic Properties and Controls Self‐Assembly of Donor/Acceptor Semiconductors

A comprehensive investigation of the complementary H‐bonding‐mediated self‐assembly between dipyrrolo[2,3‐b:3′,2′‐e]pyridine (P2P) electron donors and naphthalenediimide/perylenediimide (NDI/PDI) acceptors is reported. The synthesis of parent P2P and several aryl‐substituted derivatives is described, along with their optical, redox, and single‐crystal packing characteristics. The dual functionality of heteroatoms in the P2P/NDI(PDI) assembly, which act as proton donors/acceptors and also contribute to π‐conjugation, leads to H‐bonding‐induced perturbation of electronic levels. Concentration‐dependent NMR and UV/Vis spectroscopic studies revealed a cooperative effect of H‐bonding and π–π stacking interactions. This H‐bonding‐mediated co‐assembly of donor (D) and acceptor (A) components leads to a new charge‐transfer (CT) absorption that can be controlled throughout the visible range. The electronic interactions between D and A were further investigated by time‐dependent DFT, which provided insights into the nature of the CT transition. Electropolymerization of difuryl‐P2P afforded the first conjugated polymer incorporating H‐bonding recognition units in its main chain.     

Intermolecular Hydrogen Bonding Modulates O‐H Photodissociation in Molecular Aggregates of a Catechol Derivative

The catechol functional group plays a major role in the chemistry of a wide variety of molecules important in biology and technology. In eumelanin, intermolecular hydrogen bonding between these functional groups is thought to contribute to UV photoprotective and radical buffering properties, but the mechanisms are poorly understood. Here, aggregates of 4‐t‐butylcatechol are used as model systems to study how intermolecular hydrogen bonding influences photochemical pathways that may occur in eumelanin. Ultrafast UV‐visible and mid‐IR transient absorption measurements are used to identify the photochemical processes of 4‐t‐butylcatechol monomers and their hydrogen‐bonded aggregates in cyclohexane solution. Monomer photoexcitation results in hydrogen atom ejection to the solvent via homolytic O‐H bond dissociation with a time constant of 12 ps, producing a neutral semiquinone radical with a lifetime greater than 1 ns. In contrast, intermolecular hydrogen bonding interactions within aggregates retard O‐H bond photodissociation by over an order of magnitude in time. Excited state structural relaxation is proposed to slow O‐H dissociation, allowing internal conversion to the ground state to occur in hundreds of picoseconds in competition with this channel. The semiquinone radicals formed in the aggregates exhibit spectral broadening of both their electronic and vibrational transitions.     

芳杂环类多重氢键分子钳人工受体研究新进展

氢键是分子识别的重要推动力之一.综述了芳杂环类多重氢键分子钳人工受体研究进展.     

Routes to Hydrogen Bonding Chain‐End Functionalized Polymers

The contribution of supramolecular chemistry to polymer science opens new perspectives for the design of polymer materials exhibiting valuable properties and easier processability due to the dynamic nature of non‐covalent interactions. Hydrogen bonding polymers can be used as supramolecular units for yielding larger assemblies that possess attractive features, arising from the combination of polymer properties and the responsiveness of hydrogen bonds. The post‐polymerization modification of reactive end‐groups is the most common procedure for generating such polymers. Examples of polymerizations mediated by hydrogen bonding‐functionalized precursors have also recently been reported. This contribution reviews the current synthetic routes toward hydrogen bonding sticker chain‐end functionalized polymers.     

Impact of Hydrogen Bonding on the Fluorescence of N‐Amidinated Fluoroquinolones

The fluorescence properties of AIE‐active N‐amidinated fluoroquinolones, efficiently obtained by a perfluoroaryl azide–aldehyde–amine reaction, have been studied. The fluorophores were discovered to elicit a highly sensitive fluorescence quenching response towards guest molecules with hydrogen‐bond‐donating ability. This effect was evaluated in a range of protic/aprotic solvents with different H‐bonding capabilities, and also in aqueous media. The influence of acid/base was furthermore addressed. The hydrogen‐bonding interactions were studied by IR, NMR, UV/Vis and time‐resolved fluorescence decay, revealing their roles in quenching of the fluorescence emission. Due to the pronounced quenching property of water, the N‐amidinated fluoroquinolones could be utilized as fluorescent probes for quantifying trace amount of water in organic solvents.     

Substitution‐Controlled Excited State Processes in Heteroleptic Copper(I) Photosensitizers Used in Hydrogen Evolving Systems

Four different heteroleptic [Cu(N^N)(P^P)]PF₆ complexes, which combine classical bidentate diimine ligands and sterically demanding diphosphine ligands, are studied by a combination of ultrafast time‐resolved spectroscopy and quantum chemical calculations. The light‐induced excited state processes, accompanied by a structural change, are discussed with respect to the application of these complexes as a new class of noble‐metal‐free photosensitizers in proton reducing systems. In particular, the influence of different substituents in the ligand backbone on the photophysical properties is highlighted.