Valence tautomerism in metal complexes: Stimulated and reversible intramolecular electron transfer between metal centers and organic ligands

Among the recent developments in metal-organic frameworks (MOFs), porous layered coordination polymers (CPs) have garnered attention due to their modular nature and tunable structures. These factors enable a number of properties and applications, including gas and guest sorption, storage and separation of gases and small molecules, catalysis, luminescence, sensing, magnetism, and energy storage and conversion. Among MOFs, two-dimensional (2D) compounds are also known as 2D CPs or 2D MOFs. Since the discovery of graphene in 2004, 2D materials have also been widely studied. Several 2D MOFs are suitable for exfoliation as ultrathin nanosheets similar to graphene and other 2D materials, making these layered structures useful and unique for various technological applications. Furthermore, these layered structures have fascinating topological networks and entanglements. This review provides an overview of different aspects of 2D MOF layered architectures such as topology, interpenetration, structural transformations, properties, and applications.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications.

Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint☆

Two new CoII coordination polymers with a pyridinedicarboxylate ligand, {[Co(L)(H2O)]·H2O}n (1) and [Co3(HCOO)2(L)2(H2O)2]n (2) (H2L = 5-(pyridin-4-yl)isophthalic acid), have been synthesized and structurally characterized by elemental analysis, IR, XRPD, and single-crystal X-ray diffraction. Structure analyses show that complex 1 has a two-dimensional (2D) double-layered structure with a (3,6)-connected kgd topology based on [Co2O2] units, while complex 2 takes a three-dimensional (3D) structure with (3,6)-connected rtl topology network based on linear [Co3(HCOO)2(CO2)4] clusters with triple carboxylate bridges. Magnetic investigation indicates that besides strong spin–orbit coupling of CoII ions, ferromagnetic and weak ferromagnetic exchange interactions between CoII ions in the Co2 and Co3 clusters exist in 1 and 2, respectively. The FC/ZFC magnetization behaviors for both of them suggest the absence of any long-range magnetic ordering.

Two new CoII coordination polymers based on carboxylate-bridged di- and trinuclear clusters with a pyridinedicarboxylate ligand: synthesis, structures and magnetism

https://minerva-access.unimelb.edu.au/bitstream/handle/11343/216375/Switchable cobalt_CCR_Co_2017_revised.pdf

Switchable cobalt coordination polymers: Spin crossover and valence tautomerism

Herein reported is the first two-dimensional coordination polymer capable of undergoing thermally induced and photoinduced valence tautomeric transitions.

Thermally Induced and Photoinduced Valence Tautomerism in a Two-Dimensional Coordination Polymer

NNSF of China [90922012, 20971106, 21021061, 20923004]; Specialized Research Fund for the Doctoral Program of Higher Education [20110121110012]

Unidirectional charge transfer in di-cobalt valence tautomeric compound finely tuned by ancillary ligand.

National Natural Science Foundation of China [90922012, 20971106, 21021061]; Natural Science Foundation of Fujian Province [2009J06006]

Thermal and photoinduced valence tautomerism of a chain compound

OBJECTIVES
To estimate the system efficiency of uncle-nephew relationship identification by increasing STR markers and adding reference samples based on the test results of simulated data and real samples, so as to provide references for selecting the appropriate number of STRs and reference samples for uncle-nephew relationship identification.


METHODS
Five common models of uncle-nephew relationship identification were constructed by adding different reference samples. In each model, the likelihood ratio (LR) for 10 000 pairs of uncle-nephew relationships and 10 000 pairs of unrelated individuals were simulated by detecting 19, 39 or 55 STRs, and the system efficiency at different thresholds was simulated. The samples of the Han population in Zhejiang were collected, and 55 autosomal STRs were obtained by using SiFaSTRTM 23plex kit, Goldeneye® DNA ID 22NC kit and AGCU 21+1 PCR amplification kit. When 19, 39 and 55 STRs were detected, the LR of each model and system efficiency under different thresholds were calculated and compared with the simulation results.


RESULTS
Under the same detection system, the calculated results of simulated data and corresponding true samples were basically consistent. In the same model, there was a positive correlation between the system efficiency of uncle-nephew relationship identification and the number of STRs detected. Moreover, the system efficiency of introducing relatives was higher than identifying only two individuals. The order of preference for the introduction of relatives was the full sibling (or mother) of the uncle and the full sibling (or mother) of the nephew.


CONCLUSIONS
The system efficiency of uncle-nephew relationship identification could be improved by increasing the number of STRs and introducing known relatives, which would provide the basis for selecting the most appropriate detection system and reference individuals in actual cases.

Efficiency Analysis of Uncle-Nephew Relationship Identification by Increasing STR Markers and Adding Reference Samples.

OBJECTIVES
To study the genetic polymorphism and population genetic parameters of 16 X-STR loci in Xinjiang Uygur population.


METHODS
The Goldeneye® DNA identification system 17X was used to amplify 16 X-STR loci in 502 unrelated individuals (251 females and 251 males). The amplified products were detected by 3130xl genetic analyzer. Allele frequencies and population genetic parameters were analyzed statistically. The genetic distances between Uygur and other 8 populations were calculated. Multidimensional scaling and phylogenetic tree were constructed based on genetic distance.


RESULTS
In the 16 X-STR loci, a total of 67 alleles were detected in 502 Xinjiang Uygur unrelated individuals. The allele frequencies ranged from 0.001 3 to 0.572 4. PIC ranged from 0.568 8 to 0.855 3. The cumulative discrimination power in females and males were 0.999 999 999 999 999 and 0.999 999 999 743 071, respectively. The cumulative mean paternity exclusion chance in trios and in duos were 0.999 999 997 791 859 and 0.999 998 989 000 730, respectively. The genetic distance between Uygur population and Kazakh population was closer, and the genetic distance between Uygur and Han population was farther.


CONCLUSIONS
The 16 X-STR loci are highly polymorphic and suitable for identification in Uygur population, which can provide a powerful supplement for the study of individual identification, paternity identification and population genetics.

Li-Qin Chen

Papers

Thermally Induced and Photoinduced Valence Tautomerism in a Two-Dimensional Coordination Polymer

Unidirectional charge transfer in di-cobalt valence tautomeric compound finely tuned by ancillary ligand.

Thermal and photoinduced valence tautomerism of a chain compound

Efficiency Analysis of Uncle-Nephew Relationship Identification by Increasing STR Markers and Adding Reference Samples.

Genetic Polymorphism of 16 X-STR Loci in Xinjiang Uygur Population.