Proton-Switched Emission Behavior of Hexanuclear Molyb-denum(II) Clusters Bearing Terminal Pyridine Carboxylate Ligands

被引：10
作者：
Fujii, Sho [1 ,2 ]
Tanioka, Erina [1 ]
Sasaki, Kohei [1 ]
Horiguchi, Taishiro [1 ]
Akagi, Soichiro [1 ]
Kitamura, Noboru [1 ,3 ]
机构：
[1] Hokkaido Univ, Fac Sci, Dept Chem, Kita Ku, Kita 10,Nishi 8, Sapporo, Hokkaido 0600810, Japan
[2] Hokkaido Univ, Grad Sch Chem Sci & Engn, Kita Ku, Kita 10,Nishi 8, Sapporo, Hokkaido 0600810, Japan
[3] Toyota Phys & Chem Res Inst, Nagakute, Aichi 4801192, Japan
来源：
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2020年 / 2020卷 / 31期
关键词：
Hexanuclear molybdenum cluster; Photoluminescence; Proton responsive cluster; MOLYBDENUM(II) CHLORIDE CLUSTER; EXCITED TRIPLET-STATES; COMPLEXES; METAL; LUMINESCENT; REDOX; BR; PHOSPHORESCENCE; DEPENDENCE; SUBLEVELS;
D O I：
10.1002/ejic.202000440
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
We designed and synthesized a new and novel octahedral hexamolybdenum(II) cluster bearing terminal pyridine-3-carboxylate (3L) or pyridine-4-carboxylate ligands (4L), [{Mo6Br8}(3L)(6)](2-)(3) or [{Mo6Br8}(4L)(6)](2-)(4), to demonstrate proton-switched emission behaviour of the cluster. X-ray crystal analysis of4demonstrated that the O-atom in the carboxylate group of4Lcoordinates to each Mo atom in the {Mo6Br8}(4+)-core, indicating that the N-atom of4Lin4is open for protonation. Reflecting such structural characteristics of the cluster, both3and4showed 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.
引用
收藏
页码：2983 / 2989
页数：7
相关论文
共 59 条
[1]   Terminal Ligand (L) Effects on Zero-Magnetic-Field Splitting in the Excited Triplet States of [{Mo6Br8}L6]2- (L = Aromatic Carboxylates) [J].
Akagi, Soichiro ;
Horiguchi, Taishiro ;
Fujii, Sho ;
Kitamura, Noboru .
INORGANIC CHEMISTRY, 2019, 58 (01) :703-714
[2]   Zero-Magnetic-Field Splitting in the Excited Triplet States of Octahedral Hexanuclear Molybdenum(II) Clusters: [{Mo6X8}Y6]2-(X, Y = CI, Br, I) [J].
Akagi, Soichiro ;
Fujii, Sho ;
Kitamura, Noboru .
JOURNAL OF PHYSICAL CHEMISTRY A, 2018, 122 (46) :9014-9024
[3]   A study on the redox, spectroscopic, and photophysical characteristics of a series of octahedral hexamolybdenum(II) clusters: [{Mo6X8}Y6]2- (X, Y = Cl, Br, or I) [J].
Akagi, Soichiro ;
Fujii, Sho ;
Kitamura, Noboru .
DALTON TRANSACTIONS, 2018, 47 (04) :1131-1139
[4]   Zero-Magnetic-Field Splitting in the Excited Triplet States of Octahedral Hexanuclear Molybdenum(II) Clusters: [{Mo6X8}(n-C3F7COO)6]2- (X = Cl, Br, or l) [J].
Akagi, Soichiro ;
Sakuda, Eri ;
Ito, Akitaka ;
Kitamura, Noboru .
JOURNAL OF PHYSICAL CHEMISTRY A, 2017, 121 (38) :7148-7156
[5]   pK a(L) Dependences of Structural, Electrochemical, and Photophysical Properties of Octahedral Hexamolybdenum(II) Clusters: [Mo6 X 8 L 6]2- (X = Br or I; L = carboxylate) [J].
Akagi, Soichiro ;
Fujii, Sho ;
Horiguchi, Taishiro ;
Kitamura, Noboru .
JOURNAL OF CLUSTER SCIENCE, 2017, 28 (02) :757-772
[6]   Tuned red NIR phosphorescence of polyurethane hybrid composites embedding metallic nanoclusters for oxygen sensing [J].
Amela-Cortes, Maria ;
Paofai, Serge ;
Cordier, Stephane ;
Folliot, Herve ;
Molard, Yann .
CHEMICAL COMMUNICATIONS, 2015, 51 (38) :8177-8180
[7]   Hexacyano octahedral metallic clusters as versatile building blocks in the design of extended polymeric framework and clustomesogens [J].
Amela-Cortes, Maria ;
Cordier, Stephane ;
Naumov, Nikolay G. ;
Meriadec, Cristelle ;
Artzner, Franck ;
Molard, Yann .
JOURNAL OF MATERIALS CHEMISTRY C, 2014, 2 (46) :9813-9823
[8]   Extended Investigations on Luminescent Cs2[Mo6Br14]@SiO2 Nanoparticles: Physico-Structural Characterizations and Toxicity Studies [J].
Aubert, Tangi ;
Cabello-Hurtado, Francisco ;
Esnault, Marie-Andree ;
Neaime, Chrystelle ;
Lebret-Chauvel, Dominique ;
Jeanne, Sylvie ;
Pellen, Pascal ;
Roiland, Claire ;
Le Polles, Laurent ;
Saito, Noriko ;
Kimoto, Koji ;
Haneda, Hajime ;
Ohashi, Naoki ;
Grasset, Fabien ;
Cordier, Stephane .
JOURNAL OF PHYSICAL CHEMISTRY C, 2013, 117 (39) :20154-20163
[9]   ELECTRONIC-STRUCTURES OF THE LOWER TRIPLET SUBLEVELS OF HEXANUCLEAR MOLYBDENUM(II) CHLORIDE CLUSTER [J].
AZUMI, T ;
SAITO, Y .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (07) :1715-1721
[10]   www.nmrdb.org:: Resurrecting and processing NMR spectra on-line [J].
Banfi, Damiano ;
Patiny, Luc .
CHIMIA, 2008, 62 (04) :280-281
123456