ChemInform Abstract: Molecular Assemblies Based on Strong Axial Coordination in Metal Complexes of Saddle-Distorted Dodecaphenylporphyrins

ChemInform ◽  
2016 ◽  
Vol 47 (2) ◽  
Author(s):  
Tomoya Ishizuka ◽  
Shunichi Fukuzumi ◽  
Takahiko Kojima
Keyword(s):  
Metal Complexes ◽  
Molecular Assemblies ◽  
Axial Coordination

Molecular Assemblies of Metal Complexes via Base-Pairing of Nucleic Acids in the Crystalline State

2017 ◽  
Vol 23 (30) ◽  
pp. 7232-7237 ◽  
Author(s):  
Manabu Nakaya ◽  
Ryo Ohtani ◽  
Kunihisa Sugimoto ◽  
Masaaki Nakamura ◽  
Leonard F. Lindoy ◽  
...  
Keyword(s):  
Nucleic Acids ◽  
Metal Complexes ◽  
Crystalline State ◽  
Base Pairing ◽  
Molecular Assemblies

Molecular assemblies based on strong axial coordination in metal complexes of saddle-distorted dodecaphenylporphyrins

2015 ◽  
Vol 19 (01-03) ◽  
pp. 32-44 ◽  
Author(s):  
Tomoya Ishizuka ◽  
Shunichi Fukuzumi ◽  
Takahiko Kojima
Keyword(s):  
Electron Transfer ◽  
Metal Ions ◽  
Metal Complexes ◽  
Photoinduced Electron Transfer ◽  
Oxidation Potential ◽  
Metal Center ◽  
Lewis Acidity ◽  
Central Metal ◽  
Axial Coordination ◽  
Keggin Type

In this mini-review, we have highlighted our works on metal complexes having saddle-distorted dodecaphenylporphyrin (DPP) and its derivative as ligands in the light of enhancement of the Lewis acidity of a metal center coordinated by the porphyrin. The important point through this mini-review is ill-overlap of the out-of-plane lone pairs of pyrrole nitrogen atoms with σ-orbitals of the metal center bound to the saddle-distorted porphyrin core. The enhanced Lewis acidity of the central metal ions enabled us to construct stable molecular complexes through axial coordination using metal–DPP (M(DPP)) moieties ( M = Mo V or Sn IV ) and molecular or ionic entities with Lewis-basic coordination sites, including Keggin-type polyoxometallates (POM), which are known to have weak Lewis basicity and thus hard to coordinate to metal ions. A discrete 1:2 complex with a Ru -substituted POM performs catalytic substrate oxidation reactions in organic solvents. A 1:1 complex between Sn IV ( DPP ) and a Keggin-type POM exhibited photoinduced electron transfer, in which the Sn IV ( DPP ) moiety acts as an electron donor and the POM as an electron acceptor. Besides POM, other electron acceptors, including μ3-oxo trinuclear Ru III clusters and anthraquinone, having carboxyl groups as a linker unit also formed stable complexes with DPP-metal complexes as axial ligands to perform photoinduced electron transfer. Successful photoreactions of the M(DPP)-acceptor complexes are mainly enabled by the enhanced Lewis acidity of the DPP-metal complexes for the stabilization of the assemblies and also by lowering the oxidation potential of the porphyrin ligand to gain larger driving force of electron transfer to form an electron-transfer state with avoiding intersystem crossing. The stability and photochemical behavior are in sharp contrast to those for metal complexes with planar porphyrins as ligands.

Visualizing the coordination-spheres of photoexcited transition metal complexes with ultrafast hard X-rays

2019 ◽  
Vol 21 (18) ◽  
pp. 9277-9284 ◽  
Author(s):  
D. Khakhulin ◽  
L. M. Lawson Daku ◽  
D. Leshchev ◽  
G. E. Newby ◽  
M. Jarenmark ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
X Rays ◽  
Molecular Assemblies ◽  
Rational Development ◽  
Modern Chemistry ◽  
Coordination Spheres

The concept of coordination sphere (CS) is central to the rational development of hierarchical molecular assemblies in modern chemistry.

Frontispiece: Molecular Assemblies of Metal Complexes via Base-Pairing of Nucleic Acids in the Crystalline State

2017 ◽  
Vol 23 (30) ◽  
Author(s):  
Manabu Nakaya ◽  
Ryo Ohtani ◽  
Kunihisa Sugimoto ◽  
Masaaki Nakamura ◽  
Leonard F. Lindoy ◽  
...  
Keyword(s):  
Nucleic Acids ◽  
Metal Complexes ◽  
Crystalline State ◽  
Base Pairing ◽  
Molecular Assemblies

Metal Complexes with Macrocyclic Ligands. PartXLV Axial coordination tendency in reinforced tetraazamacrocyclic complexes

1997 ◽  
Vol 80 (3) ◽  
pp. 948-959 ◽  
Author(s):  
Ralph Kowallick ◽  
Markus Neuburger ◽  
Magareta Zehnder ◽  
Thomas A. Kaden
Keyword(s):  
Metal Complexes ◽  
Macrocyclic Ligands ◽  
Axial Coordination

Mechanochemical changes on cyclometalated Ir(iii) acyclic carbene complexes – design and tuning of luminescent mechanochromic transition metal complexes

2020 ◽  
Vol 7 (3) ◽  
pp. 786-794 ◽  
Author(s):  
Jingqi Han ◽  
Kin-Man Tang ◽  
Shun-Cheung Cheng ◽  
Chi-On Ng ◽  
Yuen-Kiu Chun ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Carbene Complexes ◽  
New Class

A new class of luminescent cyclometalated Ir(iii) complexes with readily tunable mechanochromic properties derived from the mechanically induced trans-to-cis isomerization have been developed.

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