Dalton Transactions

doi: 10.1039/c8dt90117apmid: N/A

doi: 10.1039/C8DT90117Apmid: N/A

doi: 10.1039/c8dt90118jpmid: N/A

doi: 10.1039/C8DT90118Jpmid: N/A

Chakraborty, Amit; Goura, Joydeb; Kalita, Pankaj; Swain, Abinash; Rajaraman, Gopalan; Chandrasekhar, Vadapalli

doi: 10.1039/c8dt01883apmid: 29922800

Molecular nano magnets such as single-molecule magnets (SMMs) are a class of coordination complexes with numerous potential applications such as information storage devices, Q-bits in quantum computing and spintronics materials. One of the greatest challenges in taking these molecules to end-user applications lies in devising strategies to control and predict their magnetic properties. In this regard, lanthanide-based compounds are very attractive as they possess appealing magnetic properties such as very high barriers for magnetization reversal, very large blocking temperatures etc. Controlling the microscopic energy levels of lanthanide-based single-ion magnets (SIMs) is a challenging task and to obtain molecules having very large blocking temperatures, it is desirable to enhance the ground state-excited state gap between the mJ levels and also to quench the quantum tunnelling of magnetization that often circumvents the barrier height. One of the strategies that has been developed by us and others in this area is to employ a diamagnetic transition metal ion to achieve this goal. Over the years several diamagnetic ions such as ZnII, NiII (square planar), AlIII and CoIII have been successfully employed to obtain lanthanide-based SMMs with interesting properties. In this perspective, we discuss how incorporation of diamagnetic ion(s) in the cluster aggregation enhances the barrier height for magnetization reversal and hence improves the magnetic properties. We also discuss theoretical studies on such systems based on ab initio calculations performed using CASSCF level of theory. Such studies are helpful in affording an understanding of the role and limitation of the diamagnetic ions in enhancing the barrier height for magnetization reversal of molecular nanomagnets.

Hao, Zhi-Min; Chao, Meng-Yao; Liu, Yan; Song, Ying-Lin; Yang, Jun-Yi; Ding, Lifeng; Zhang, Wen-Hua; Lang, Jian-Ping

doi: 10.1039/c8dt02080apmid: 29915847

Five stable clusters sharing the cuboidal [Ni4O4] skeleton are subjected to third-order nonlinear optical (NLO) property measurements. Preliminary results suggest that the NLO property is largely defined by the cluster core skeleton and the directly coordinated atoms, with limited contribution from the heavy atoms peripherally attached to the aromatic ligands.

Khan, Malik Dilshad; Murtaza, Ghulam; Revaprasadu, Neerish; O'Brien, Paul

doi: 10.1039/c8dt00953hpmid: 29916514

Xanthate complexes are used in the low temperature atom efficient synthesis of some geological and technologically important ternary compounds. The process involves direct heating of a stoichiometric mixture of the metal xanthate complexes. The reactive melts of the xanthates, generated in the transition state, cleanly decompose to ternary metal sulfides. The method has great potential for the facile scalable synthesis of ternary materials of composition ABX2 (such as AI = Ag, Cu; BIII = Bi, Cr, Fe, In, Sb and X = S) or AB2X4 (AII = Cd, Co, Cu, Ni; BIII = Co, Cr, Ni, Fe, and X = S).

Zhai, Yuan-Qi; Deng, Yi-Fei; Zheng, Yan-Zhen

doi: 10.1039/c8dt01683fpmid: 29922787

Two mononuclear pseudotetrahedral cobalt(ii) complexes with the formula Co(PNP)X2, where X = Cl (1) or X = SCN (2) and PNP = bis(2-(diphenylphosphaneyl)-4-methylphenyl)amine, have been synthesised. Magnetic and high-frequency/field electron paramagnetic resonance (HF-EPR) spectroscopy and ab initio calculation studies reveal that both complexes show uniaxial magnetic anisotropy.

Hinz, Alexander; Goicoechea, Jose M.

doi: 10.1039/c8dt01993bpmid: 29932196

The synthesis of a novel heterocubane [RSnE]4 was successful for E = As, while for E = P differing behaviour was observed. Aryl-substituted chlorostannylenes were treated with salts of heavy cyanate homologues PCO− and AsCO−. The reaction with AsCO− salts afforded primarily [TerSnAs]4 (Ter = 2,6-dimesitylphenyl). In contrast, the reaction of TerSnCl with NaPCO proceeded considerably less cleanly affording a mixture of products. The main product was putatively a neutral [Ter4Sn4P4] compound, however, it is not a cubane. A variety of by-products of this reaction could be characterised crystallographically.

Todisco, Stefano; Saielli, Giacomo; Gallo, Vito; Latronico, Mario; Rizzuti, Antonino; Mastrorilli, Piero

doi: 10.1039/c8dt01561apmid: 29845184

31P and 195Pt solid state NMR spectra of anti-[(PHCy)ClPt(μ-PCy2)2Pt(PHCy)Cl] (3) and [(PHCy2)Pt(μ-PCy2)(κ2P,O-μ-POCy2)Pt(PHCy2)] (Pt–Pt) (4) were recorded under cross polarization/magic-angle spinning conditions (31P) or with the cross polarization/Carr–Purcell–Meiboom–Gill pulse sequence (195Pt) and compared to the data obtained by relativistic DFT calculations of 31P and 195Pt CS tensors and isotropic shielding at the ZORA spin–orbit level. A good agreement with the experimental results was found and it was possible to rationalize the chemical shift differences of 195Pt and 31P nuclei between compounds 3 and 4 as mostly due to a change (in opposite directions for 195Pt and 31P) of the principal component of the shielding tensor perpendicular to the molecular plane defined by the Pt and P atoms. Paramagnetic and spin–orbit terms were found to be the most important contributions to 195Pt and 31P shielding.