The stability of a photoactivated isonitrosyl state was boosted by confining a pre-designed bicarboxylate ligand with a ruthenium nitrosyl fragment in a 2D metal-organic framework. The novel Zn/Ru-based MOF, {Zn[RuNO(HO)(inic)(OH)]}·12HO (inic = isonicotinate), was obtained with enhanced isonitrosyl stability by 30 K (up to 200 K) compared to the related ruthenium-only complex.
Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, College of Chemistry and Materials Science, Jinan University, Guangzhou 510632, P. R. China.
Herein we report two tubular metal-organic cages (MOCs), synthesized by the self-assembly of bidentate metalloligands with different lengths and Pd. These two MOCs feature PdL-type square tubular and PdL-type triangular cage structures, respectively. Both MOCs have been fully characterized by NMR spectroscopy, mass spectrometry, and theoretical calculation.
This article discusses the design principles and strategies and the structural outcome of various supramolecular architectures constructed by utilizing well-defined coordination complexes as the metalloligands. We have included selected examples of metalloligands, offering either pyridyl or arylcarboxylic acid groups as the appended functional groups, for illustrating the construction of their supramolecular architectures. Both geometrical position and the number of the appended functional groups emerging from a metalloligand were found to critically regulate the structural aspects and dimensionality of the resultant material.
The stability of a photoactivated isonitrosyl state was boosted by confining a pre-designed bicarboxylate ligand with a ruthenium nitrosyl fragment in a 2D metal-organic framework. The novel Zn/Ru-based MOF, {Zn[RuNO(HO)(inic)(OH)]}·12HO (inic = isonicotinate), was obtained with enhanced isonitrosyl stability by 30 K (up to 200 K) compared to the related ruthenium-only complex.
A visible light absorbing [RuII(tpy)2]2+-type chromophore appended with a dipicolinic acid LnIII chelator has been prepared and complexed with several differing lanthanide cations to form the corresponding heterobimetallic d-f assemblies. The subseqent solution speciation analysed by 1H NMR spectroscopy revealed an unexpected decrease in the LnIII chelate complex stability, in particular for the 1 : 3 complex, when compared to the parent dipicolinic acid. As a result, the desired Ln(ML)3 complexes could not be isolated, and the 1 : 1 LnIII-ML complexes were instead characterised and investigated using steady state absorption and emission spectroscopy.
MOE Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, and School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou, 510275, China.
The photoinduced regio- and enantioselective coupling of naphthols and derivatives thereof is achieved in the confined chiral coordination space of a Ru metalloligand based cage. The racemic or enantiopure cages encapsulate naphthol guests, which then undergo a regiospecific 1,4-coupling, rather than the normal 1,1-coupling, to form 4-(2-hydroxy-1-naphthyl)-1,2-napthoquinones; moderate stereochemical control is achieved with homochiral cages. The photoreactions proceed under both aerobic and anaerobic conditions but through distinct pathways that nevertheless involve the same radical intermediates.
