In Situ X-Ray Techniques Unraveling Charge Distribution Induced by Halogen Bonds in Solvates of an Iodo-Substituted Squaraine Dye.

The importance of halogen bonds (XBs) in the regulation of material properties through a variation in the electrostatic potential of the halogen atom is not attracted much attention. Herein, this study utilizes in situ single crystal X-ray diffraction and synchrotron-based X-ray techniques to investigate the cooling-triggered irreversible single-crystal-to-single-crystal transformation of the DMF solvated iodo-substituted squaraine dye (SQD-I). Transformation is observed to be mediated by solvent-involved XB formation and strengthening of electrostatic interaction between adjacent SQD-I molecules. By immersing a DMF solvate in acetonitrile a solvent exchange without loss of long-range ordering is observed. This is attributed to conservation of the molecular charge distribution of SQD-I molecules during the process. The different solvates can be used in combination for temperature-dependent image encryption. This work emphasizes the changes caused by XB formation to the electrostatic potentials of halogen containing molecules and their influence on material properties and presents the potential utility of XBs in the design of soft-porous crystals and luminescent materials.

Precise peripheral design enables propeller-like squaraine dye with highly sensitive and wide-range piezochromism.

Piezochromic fluorescent (PCF) materials that feature high sensitivity and wide-range switching are attractive in intelligent optoelectronic applications but their fabrication remains a significant challenge. Here we present a propeller-like squaraine dye SQ-NMe2 decorated with four peripheral dimethylamines acting as electron donors and spatial obstacles. This precise peripheral design is expected to loosen the molecular packing pattern and facilitate more substantial intramolecular charge transfer (ICT) switching caused by conformational planarization under mechanical stimuli. As such, the pristine SQ-NMe2 microcrystal exhibits significant fluorescence changes from yellow (λem = 554 nm) to orange (λem = 590 nm) upon slight mechanical grinding and further to deep red (λem = 648 nm) upon heavy mechanical grinding. Single-crystal X-ray diffraction structural analysis of two SQ-NMe2 polymorphs provides direct evidence to illustrate the design concept of such a piezochromic molecule. The piezochromic behavior of SQ-NMe2 microcrystals is sensitive, high-contrast, and easily reversible, enabling cryptographic applications.

Saturated Coordination LuN6 Defect Sites for Highly Efficient Electroreduction of CO2.

Metal single-atom and internal structural defects typically coexist in M-N-C materials obtained through the existing basic pyrolysis processes. Identifying a correlation between them to understand the structure-activity relationship and achieve efficient catalytic performance is important, particularly for the rare-earth (RE) elements with rich electron orbitals and strong coordination capabilities. Herein, a novel single-atom catalyst based on the RE element lutetium is successfully synthesized on a N-C support. Structural and simulation analyses demonstrate that the formation of a LuN6 structural site with an individual defect because of pyrolysis is thermodynamically favorable in Lu-N-C. Using KHCO3 -based electrolytes facilitates the fall of the K+ cations into the defective sites of Lu-N-C, thus enabling improved CO2 capture and activation, which increases the catalyst conductivity for Lu-N-C. In this study, the catalyst exhibits a Faradaic efficiency of 95.1% for CO at a current density of 18.2 mA cm-2 during carbon dioxide reduction reaction. This study thus provides new insights into understanding RE-N-C materials for energy utilization.

Multilayer-Cavity Tandem Catalyst for Profiling Sequentially Coupling of Intermediate CO in Electrocatalytic Reduction Reaction of CO2 to Multi-Carbon Products.

Electrochemical CO2  reduction reaction (CO2 RR) is an effective approach to address CO2  emission, promote recycling, and synthesize high-value multi-carbon (C2+ ) chemicals for storing renewable electricity in the long-term. The construction of multilayer-bound nanoreactors to achieve management of intermediate CO is a promising strategy for tandem to C2+ products. In this study, a series of Ag@Cu2 O nanoreactors consisting of an Ag-yolk and a multilayer confined Cu shell is designed to profile electrocatalytic CO2 RR reactions. The optimized Ag@Cu2 O-2 nanoreactor exhibits a 74% Faradaic efficiency during the C2+ pathway and remains stable for over 10 h at a bias current density of 100 mA cm-2 . Using the finite element method, this model determines that the certain volume of cavity in the Ag@Cu2 O nanoreactors facilitates on-site CO retention and that multilayers of Cu species favor CO capture. Density functional theory calculations illustrate that the biased generation of ethanol products may arise from the (100)/(111) interface of the Cu layer. In-depth explorations in multilayer-bound nanoreactors provide structural and interfacial guidance for sequential coupling of CO2 RR intermediates for efficient C2+ generation.

Maximal emission beyond 1200 nm dicyanovinyl-functionalized squaraine for in vivo vascular imaging.

The first maximum emission wavelength beyond 1200 nm acceptor-substituted squaraine fluorophore with ultra-high brightness and photostability has been developed. It can be co-assembled with bovine serum albumin to form an excellent biocompatible dye-protein nanocomplex with significant fluorescence enhancement for high-resolution vascular imaging.

Triphenylamine-equipped 1,8-naphthaolactam: a versatile scaffold for the custom design of efficient subcellular imaging agents.

Fluorescence imaging has enabled much progress in biological fields, while the evolution of commercially available dyes has lagged behind their advanced applications. Herein, we launch triphenylamine-equipped 1,8-naphthaolactam (NP-TPA) as a versatile scaffold for the custom design of an efficient subcellular imaging agent (NP-TPA-Tar), given its bright and constant emissions in various states, significant Stokes shifts, and facile modifiability. The resultant four NP-TPA-Tars maintain excellent emission behavior with targeted modifications and can map the spatial distribution of lysosomes, mitochondria, endoplasmic reticulum, and plasma membrane in Hep G2 cells. Compared to its commercial counterpart, NP-TPA-Tar has a 2.8-25.2 fold increase in Stokes shift, a 1.2-1.9 fold increase in photostability, enhanced targeting capability, and comparable imaging efficiency even at low concentrations of 50 nM. This work will help to accelerate the update of current imaging agents and super-resolution and real-time imaging in biological applications.

A squaraine-based fluorescence turn on chemosensor with ICT character for highly selective and sensitive detection of Al3+ in aqueous media and its application in living cell imaging.

A novel and simple squaraine-based fluorescent chemosensor SQ-BH bearing the benzoylhydrazine moiety was developed for the highly sensitive and selective detection of Al3+ in methanol-water mixture. The chemosensing behaviors of SQ-BH and its binding interaction with Al3+ were explored by various spectroscopic analyses. The reversibility of Al3+ recognition process was investigated using EDTA. The results of experiments and DFT/TDDFT calculations revealed that the chemosensor SQ-BH obeyed a turn on mechanism which was associated with the inhibited photoinduced electron transfer (PET), the enhanced intramolecular charge transfer (ICT) and the activated chelation enhanced fluorescence (CHEF). Furthermore, the fluorescent chemosensor SQ-BH whose excellent biocompatibility was confirmed by a standard MTT assay could be used to detect Al3+ in living cells, indicating its potential application value in biological fields.

Excited state intramolecular single proton transfer mechanism of pigment yellow 101 in solid state: Experiment and DFT calculation.

To investigate fluorescence mechanism of Pigment Yellow 101 (P. Y. 101) in solid state, three aromatic aldehyde azines (1-3) including P. Y. 101 have been synthesized and compared with each other. Results indicated that P. Y. 101 prepared by solvothermal method is actually the mixture of two polymorphs, whose molecular packing mode can be transformed into each other by recrystallizing or external stimuli such as pressure and grinding. The ESIPT properties of 1-3 were investigated by DFT/TD-DFT calculations and time-correlated single photon counting (TCSPC) technique. Both experimental and theoretical results revealed that the dual fluorescence properties of P. Y. 101 in solid state are ascribed to the excited-state intramolecular single proton transfer fluorescence emissions of two structurally different polymorphs rather than the results of the sequential or concerted excited-state intramolecular double proton transfers, which provide a potential valuable tool for developing multistimuli-responsive luminescent materials.

Controlling Crystal Structures and Multiple Thermo- and Vapochromic Behaviors of Benzimidazole-Based Squaraine Dyes by Molecular Design and Solvent Adjustment.

Organic micro- and nanostructures are expected to be promising candidates for micro- and nanophotonic materials with desirable properties owing to their low cost, flexible molecular design, and tunable self-assembly. Among these candidates, well-known squaraine dyes (SQs) have rarely been investigated because of their nonfluorescent properties in the solid state and because their optical behavior varies with changes in morphology. In this contribution, two novel 1,2-SQs, SQM and SQB, with strong bright-yellow to red fluorescence emission in the crystalline state, were designed and structured at the molecular level and by solvent adjustment. Their self-assembly behavior was studied, and it was revealed that the SQM assembly provided 1D microrods, whereas 1D microrods (Z-SQB⋅CH2 Cl2 ) and 2D microplates (E-SQB⋅2 CH3 OH) could be obtained from SQB assemblies through a solution-based self-assembly method. The varied assembly behaviors of these SQs were attributed to different π-π stacking interactions that resulted in different molecular conformations and packing modes. These assemblies exhibited distinct optical properties, and in particular, SQB⋅solvent assemblies showed multiple thermo- and vapochromic effects. Thus, the SQB assemblies are potential fluorescent sensors for organic solvent vapors. More importantly, favorable optical-waveguide properties were observed in these SQ-based microstructures.

A novel non-fluorescent excited state intramolecular proton transfer phenomenon induced by intramolecular hydrogen bonds: an experimental and theoretical investigation.

Two molecules, 1-hydroxypyrene-2-carbaldehyde (HP) and 1-methoxypyrene-2-carbaldehyde (MP) were explored. We investigated their photophysical properties, using experimental transient absorption and theoretical density functional theory/time-dependent density functional theory (DFT/TDDFT). HP and MP have similar geometric conformations but exhibit entirely different photophysical properties upon excitation into the S1 state. In contrast to traditional excited state intramolecular proton transfer (ESIPT) in molecules that exhibit either single or dual fluorescence, HP has an unusual non-fluorescent property. Specifically, the ultrafast ESIPT process occurs in 158 fs and is followed by an intersystem crossing (ISC) component of 11.38 ps. In contrast to HP, MP undergoes only an 8 ps timescale process, which was attributed to interactions between solute and solvent. We concluded that this difference arises from intramolecular hydrogen bonds (IMHBs), which induce drastic structural alterntion upon excitation.

A squaraine-based colorimetric and F(-) dependent chemosensor for recyclable CO2 gas detection: highly sensitive off-on-off response.

An unsymmetrical squaraine-based chemosensor SH2 has been synthesized, and its sensing behavior towards CO2 gas was described in detail by UV-vis and (1)H NMR spectroscopies in DMSO. The results indicated that the extremely sensitive "naked-eye" CO2 gas detection can be operated in the presence of excess [Bu4N]F (TBAF) and the sensor is easy to recycle. These properties enable SH2 to act as a CO2 and F(-) controlled "OFF-ON-OFF" switch. Combining theoretical analyses, a plausible sensing mechanism was proposed to illustrate how the receptor SH2 works as a CO2 sensitive and selective colorimetric probe in the present system.

Highly sensitive detection of carbon dioxide by a pyrimido[1,2-a]benzimidazole derivative: combining experimental and theoretical studies.

In the present paper, a "light-up" chemsensor with a high specificity for carbon dioxide detection using a pyrimido[1,2-a]benzimidazole derivative (P1H) in liquid media has been developed. The results show that P1H reacts with carbon dioxide activated by a basic ion to form a carboxylic acid compound (P1-COOH). These results also provide a possible method for carboxylation reactions of P1H using carbon dioxide based on a vinyl carbanion. The complete reaction mechanism cycle was also described using DFT calculations.