02271nas a2200181   4500008004100000022001400041245007900055210006900134260011000203300001600313490000700329520156600336100002601902700001401928700001801942700001901960856011001979       2015                        eng d  a1477-922600aCations and dications of heavier group 14 elements in low oxidation states0 aCations and dications of heavier group 14 elements in low oxidat  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN  a12903-129230 v443 a<p>Cations and dications of heavier group 14 elements in their low oxidation state have received widespread attention in recent years. The journey started with the isolation of a series of cations of the composition [(C5Me5)E:](+) [E = Si-Pb], followed by the more recent isolation of a Ge(II) dication encapsulated within a cryptand, a carbodiphosphorane stabilized [GeCl](+) monocation with a two coordinate Ge atom, Si(II) cations and dications stabilized by N-heterocyclic carbenes (NHCs), which highlights the ongoing growth and interest in the chemistry of tetrel(II) cations. This is presumably because the central atom (E) in these compounds contains two or three unoccupied valence orbitals as well as holds a lone pair of electrons. Such an electronic description represents ambiphilicity, which is of great interest for catalysis. The successful synthesis of divalent group 14 cations requires new synthetic strategies based on the sterically demanding neutral or monoanionic ligands, utilization of counter anions, and solvents with low nucleophilicity in order to minimize the degree of interactions with the cations. An alternative approach for the realization of divalent cations of group 14 elements is their coordination to the transition metals. This synthetic approach was successfully applied for the isolation of a range of transition metal coordinated divalent cations of group 14 elements. Apart from arousing academic interest some of these cations have found application as activators in the Ziegler-Natta polymerization of alkenes.</p>1 aSwamy, V., S. V. S. N1 aPal, Shiv1 aKhan, Shabana1 aSen, Sakya, S.  uhttps://library.ncl.res.in/content/cations-and-dications-heavier-group-14-elements-low-oxidation-states-001375nas a2200205   4500008004100000022001400041245006500055210006300120260011000183300001400293490000700307520065500314100002600969700001900995700001401014700001501028700001701043700001901060856009001079       2016                        eng d  a1359-734500aFacile access to a Ge(II) dication stabilized by isocyanides0 aFacile access to a GeII dication stabilized by isocyanides  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAY  a7890-78920 v523 a<p>Herein, we introduce isocyanide as a ligand in main group chemistry and describe the facile isolation of a Ge(II) dication. The reaction of 2,6-dimethylphenylisocyanide with GeCl2 leads to the formation of a Ge(II) dication with two [GeCl3](-) molecules as counter anions. The dicationic Ge(II) center is bound to four isocyanide ligands and also holds a lone pair of electrons. DFT calculations reveal that the dication is stabilized only by sigma-donation from the four isocyanide ligands. Natural population analysis gives a charge of +0.74 on the Ge(II) center, indicating that the positive charge is shared by the isocyanide substituents.</p>1 aSwamy, V., S. V. S. N1 aYadav, Sandeep1 aPal, Shiv1 aDas, Tamal1 aVanka, Kumar1 aSen, Sakya, S.  uhttps://library.ncl.res.in/content/facile-access-geii-dication-stabilized-isocyanides01241nas a2200181   4500008004100000245008400041210006900125260000800194300001400202490000700216520062600223100002000849700002300869700001400892700001900906700001800925856011600943       2017                        eng d00aStrikingly diverse reactivity of structurally identical silylene and stannylene0 aStrikingly diverse reactivity of structurally identical silylene  cMAY  a6528-65320 v463 aThe reactivity of structurally identical silylene and stannylene [PhC(NtBu)(2)EN(SiMe3)(2)] (E = Si (1) and Sn (2)) towards coinage metals has been explored. While 1 has the propensity to form an adduct with coinage metals (4 and 5), 2 undergoes a ligand exchange reaction with copper halides and silver triflate leading to PhC(NtBu) 2SnX (X = Br (6), Cl (7), and OSO2CF3 (8)) with concomitant formation of [M{N(SiMe3) (2)}] (M = Cu, Ag). However, with AgSbF6 both 1 and 2 led to ion pairs, 9(+) .SbF(6)(-)and 10(+) . SbF(6)(-)displaying weaker Ag center dot center dot center dot center dot F interactions in the latter.1 aParvin, Nasrina1 aDasgupta, Rajarshi1 aPal, Shiv1 aSen, Sakya, S.1 aKhan, Shabana  uhttps://library.ncl.res.in/content/strikingly-diverse-reactivity-structurally-identical-silylene-and-stannylene02140nas a2200313   4500008004100000022001400041245013500055210006900190260000900259300001600268490000700284520108400291653001901375653004001394653002201434653001901456653001601475100001701491700002501508700001401533700001801547700001601565700002001581700003101601700002301632700002301655700002501678856012301703       2021                        eng d  a1433-785100aOrganic-inorganic perovskitoid with zwitterion cysteamine linker and its crystal-crystal transformation to ruddlesden-popper phase0 aOrganicinorganic perovskitoid with zwitterion cysteamine linker   cAUG   a18750-187600 v603 aWe demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.10aCrystal growth10aorganic-inorganic hybrid composites10aperovskite phases10aphotodetectors10azwitterions1 aKour, Prachi1 aReddy, Mallu, Chenna1 aPal, Shiv1 aSidhik, Siraj1 aDas, Tisita1 aPandey, Padmini1 aMukherjee, Shatabdi, Porel1 aChakraborty, Sudip1 aMohite, Aditya, D.1 aOgale, Satishchandra  uhttps://library.ncl.res.in/content/organic-inorganic-perovskitoid-zwitterion-cysteamine-linker-and-its-crystal-crystal