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Proton‐Switched Emission Behavior of Hexanuclear Molyb‐denum(II) Clusters Bearing Terminal Pyridine Carboxylate Ligands
Author(s) -
Fujii Sho,
Tanioka Erina,
Sasaki Kohei,
Horiguchi Taishiro,
Akagi Soichiro,
Kitamura Noboru
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000440
Subject(s) - chemistry , protonation , carboxylate , pyridine , cluster (spacecraft) , crystallography , octahedron , proton , atom (system on chip) , crystal structure , stereochemistry , medicinal chemistry , ion , organic chemistry , quantum mechanics , computer science , programming language , embedded system , physics
We designed and synthesized a new and novel octahedral hexamolybdenum(II) cluster bearing terminal pyridine‐3‐carboxylate ( 3L ) or pyridine‐4‐carboxylate ligands ( 4L ), [{Mo 6 Br 8 }( 3L ) 6 ] 2– ( 3 ) or [{Mo 6 Br 8 }( 4L ) 6 ] 2– ( 4 ), to demonstrate proton‐switched emission behaviour of the cluster. X‐ray crystal analysis of 4 demonstrated that the O‐atom in the carboxylate group of 4L coordinates to each Mo atom in the {Mo 6 Br 8 } 4+ ‐core, indicating that the N‐atom of 4L in 4 is open for protonation. Reflecting such structural characteristics of the cluster, both 3 and 4 showed proton‐switched emission behaviour owing to the changes in the electron‐donating abilities of the relevant terminal ligands upon protonation to the pyridine N atoms: blue shifts of the emission spectra and increases in the emission lifetimes of the clusters.