Resonance induced proton transfer leading to NIR emission in coumarin thiazole hybrid dyes: Synthesis and DFT insights

We present a bioinspired strategy for enhancing electrochemical carbon dioxide reduction catalysis by cooperative use of base-metal molecular catalysts with intermolecular second-sphere redox mediators that facilitate both electron and proton transfer. Functional synthetic mimics of the biological redox cofactor NADH, which are electrochemically stable and are capable of mediating both electron and proton transfer, can enhance the activity of an iron porphyrin catalyst for electrochemical reduction of CO2 to CO, achieving a 13-fold rate improvement without altering the intrinsic high selectivity of this catalyst platform for CO2 versus proton reduction. Evaluation of a systematic series of NADH analogs and redox-inactive control additives with varying proton and electron reservoir properties reveals that both electron and proton transfer contribute to the observed catalytic enhancements. This work establishes that second-sphere dual control of electron and proton inventories is a viable design strategy for developing more effective electrocatalysts for CO2 reduction, providing a starting point for broader applications of this approach to other multi-electron, multi-proton transformations.

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An Alternate Energy-Conserved Pathway for the Morita-Baylis-Hillman (MBH) Reaction

10.26434/chemrxiv.12011673.v1 ◽

2020 ◽

Author(s):

Veejendra Yadav

Keyword(s):

Proton Transfer ◽

Transition State ◽

Lower Energy ◽

Aldol Reaction ◽

Membered Ring ◽

Ammonium Ion ◽

Alternate Energy ◽

Ring Transition State ◽

Mbh Reaction

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.

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An Alternate Energy-Conserved Pathway for the Morita-Baylis-Hillman (MBH) Reaction

10.26434/chemrxiv.12011673 ◽

2020 ◽

Author(s):

Veejendra Yadav

Keyword(s):

Proton Transfer ◽

Transition State ◽

Lower Energy ◽

Aldol Reaction ◽

Membered Ring ◽

Ammonium Ion ◽

Alternate Energy ◽

Ring Transition State ◽

Mbh Reaction

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.

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Highly Fluorescent Au25-xAgx Nanoclusters Protected with Poly(ethylene glycol) - and Zwitterion-Modified Thiolate Ligands

10.26434/chemrxiv.6987479 ◽

2018 ◽

Author(s):

Dinesh Mishra ◽

Sisi Wang ◽

Zhicheng Jin ◽

Eric Lochner ◽

Hedi Mattoussi

Keyword(s):

Quantum Yield ◽

Near Infrared ◽

Small Diameter ◽

Binding Energies ◽

Thiolate Ligands ◽

Nir Emission ◽

Thiolate Complexes ◽

Long Lifetime ◽

Poly Ethylene

We describe the growth and characterization of highly fluorescing, near-infrared-emitting nanoclusters made of bimetallic Au25-xAgx cores, prepared using various monothiol-appended hydrophobic and hydrophilic ligands. The reaction uses well-defined triphenylphosphine-protected Au11 clusters (as precursors), which are reacted with Ag(I)-thiolate complexes. The prepared nanoclusters are small (diameter < 2nm, as characterized by TEM) with emission peak at 760 nm and long lifetime (~12 µs). The quantum yield measured for these materials was 0.3 - 0.4 depending on the ligand. XPS measurements show the presence of both metal atoms in the core, with measured binding energies that agree with reported values for nanocluster materials. The NIR emission combined with high quantum yield, small size and ease of surface functionalization afforded by the coating, make these materials suitable to implement investigations that address fundamental questions and potentially useful for biological sensing and imaging applications.

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