Surface directed reversible imidazole ligation to nickel(ii) octaethylporphyrin at the solution/solid interface: a single molecule level study
Literature Information
Goutam Nandi, Bhaskar Chilukuri, K. W. Hipps, Ursula Mazur
Scanning tunneling microscopy (STM) is used to study for the first time the reversible binding of imidazole (Im) and nickel(II) octaethylporphyrin (NiOEP) supported on highly oriented pyrolytic graphite (HOPG) at the phenyloctane/NiOEP/HOPG interface at 25 °C. The ligation of Im to the NiOEP receptor while not observed in fluid solution is readily realized at the solution/HOPG interface. The coordination process scales with increasing Im concentration and can be effectively modeled by the Langmuir isotherm. At room temperature it is determined that the standard free energy of adsorption is ΔGc = −15.8 kJ mol−1 and the standard enthalpy of adsorption is estimated to be ΔHc ≈ −80 kJ mol−1. The reactivity of imidazole toward NiOEP adsorbed on HOPG is attributed to charge donation from the graphite stabilizing the Im–Ni bond. This charge transfer pathway is supported by molecular and periodic modeling calculations which indicate that the Im ligand behaves as a π-acceptor. DFT calculations also show that the nickel ion in the Im–NiOEP/HOPG complex is in a singlet ground state. This is surprising since both our calculations and previous experimental studies find a triplet ground state for the five and six coordinated Im–nickel(II) porphyrins in the gas-phase or in solution. Both the experimental and the theoretical findings provide information that is useful for better understanding of chemical sensing/recognition and catalytic processes that utilize metal–organic complexes adsorbed on surfaces where the reactivity of the metal is moderated by the substrate.
Related Literature
You might also like
How should waste containing N-Methoxy-N-methyl-1,3-thiazole-5-carboxamide (CAS: 898825-89-3) be handled?
Waste containing N-Methoxy-N-methyl-1,3-thiazole-5-carboxamide (CAS: 898825-89-3...
How should N-(4-Biphenylyl)dibenzo[b,d]furan-4-amine (CAS: 1318338-47-4) be stored?
N-(4-Biphenylyl)dibenzo[b,d]furan-4-amine should be stored in a tightly sealed c...
What is the market or research trend for 3-Acetamido-5-amino-2,4,6-triiodobenzoic acid (CAS: 1713-07-1)?
The market for 3-Acetamido-5-amino-2,4,6-triiodobenzoic acid (CAS: 1713-07-1) is...
How should Benzyl 2-O-acetyl-3,4,6-tri-O-benzyl-beta-D-galactopyranoside (CAS: 61820-03-9) be stored?
Benzyl 2-O-acetyl-3,4,6-tri-O-benzyl-beta-D-galactopyranoside (CAS: 61820-03-9) ...
What regulatory guidelines apply to 2-Ethylpiperazine dihydrochloride (CAS: 438050-52-3)?
2-Ethylpiperazine dihydrochloride (CAS: 438050-52-3) is regulated under the Glob...
What regulatory guidelines apply to 1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) (CAS: 119462-56-5)?
1,1'-[1,3-Phenylenebis(methylene)]bis(3-methyl-1H-pyrrole-2,5-dione) (CAS: 11946...
Are there alternatives to 5-Fluoro-2-(1-pyrrolidinyl)pyridine (CAS: 1287217-79-1) in synthesis?
Several alternatives can be used in the synthesis of 5-Fluoro-2-(1-pyrrolidinyl)...
What precautions should be taken when handling 1-((2R,3R,4R,5R)-5-((bis(4-methoxyphenyl)(phenyl)methoxy)methyl)-4-hydroxy-3-methoxytetrahydrofuran-2-yl)-5-methylpyrimidine-2,4(1H,3H)-dione (CAS: 153631-19-7)?
Proper personal protective equipment (PPE) must be worn when handling this compo...
What precautions should be taken when handling 6-Bromoimidazo[1,2-a]pyridin-8-amine (CAS: 676371-00-9)?
When handling 6-Bromoimidazo[1,2-a]pyridin-8-amine, it is important to wear appr...
Are there alternatives to (2S,4R)-4-(4-Nitrobenzyl)pyrrolidine-2-carboxylic acid hydrochloride (CAS: 1049740-22-8) in synthesis?
Alternatives to (2S,4R)-4-(4-Nitrobenzyl)pyrrolidine-2-carboxylic acid hydrochlo...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










![[(5-Methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetic acid structure [(5-Methyl-1,3,4-thiadiazol-2-yl)sulfanyl]acetic acid structure](https://static.chemtradehub.com/structs/509/50918-26-8-4ce8.webp)


![2-(7,7-Difluorobicyclo[4.1.0]hept-1-yl)ethanamine structure 2-(7,7-Difluorobicyclo[4.1.0]hept-1-yl)ethanamine structure](https://static.chemtradehub.com/structs/209/2098065-08-6-ff24.webp)
