In Situ Two-Step Crystallization: Transformation of Kinetic Crystals into Thermodynamic Crystals

Abstract

Unusual in situ two-step crystallization on self-assembly of AgX (X– = CF3SO3 – and PF6 –) with 1,3,5-tris­(nicotinoyloxy-methyl)­benzene (L) has been carried out. The self-assembly reaction produces initial single crystals consisting of cyclophane-type 30-membered macrocyclic linked one-dimensional (1D) coordination polymers, and then the single crystals are transformed into different morphological crystals consisting of 16-membered macrocyclic linked 1D coordination polymers in the mother liquor. The crystal structures show significant difference in metallophilicity between CF3SO3 – and PF6 – anion.

Coordinating Ability of Anions, Solvents, Amino Acids, and Gases towards Alkaline and Alkaline‐Earth Elements, Transition Metals, and Lanthanides

“…[18] In another case, the indices were used to explain the different roles played by two anionsi nt he self-assembly of AgX with at ridentate ligand:w hile for X = triflate the anion is coordinated, when hexafluorophosphatei su sed instead, it remains as a non-coordinated counterion. [19] Analogous approaches have been applied by other researchers when studying substitution reactions. [20,21] Also ac ationic Ta complex with coordinated water hasb een seen to be stable when obtained as the triflate salt, butt od ecompose readily in solution in the presence of the less coordinating BF 4 À and [BMe(C 6 F 5 ) 3 ] À ions.…”

“…However, for the two solvents involved, the coordination ability indices deduced here for the specific case of Sn appear to follow the same sequence, with a Sn = À0.6 and À1.5 for THF and benzene, respectively.I na nother NMR experiment, the choice of MeOD as as olvent was also based on its coordination ability index. [66] The 19 FN MR spectra of aW -calixarene-imido complex in the presence of av ariety of analytes, show only one triplet with ethanol, ethyl acetate, and acetone( a TM = À0.5, À0.8 and À1.0, respectively), which suggestedt hat these analytes do not bond strongly to tungsten and/or that the binding is too dynamic to induce ashift in the spectrum. In contrast in the presence of alarge excess of ethanol, an upfield shift was observed which can be considered as as olvente ffect.…”

“…An ew upfield peak was observed in the experiment with DMSO (a TM = 0.2), indicating the association of DMSO in solution. The effect of other solvents (MeCN and DMF, a TM = À0.2) on the 19 FNMR spectra wasalso discussed. [67] The spectroscopic (XAS and UV/Vis) features of two Cu II compounds have been seen to be highly solventd ependent.…”

“…The coordination indices have been applied to rationalize synthetic results, such as the replacement of the trifluoroacetate ion from the coordination sphere of a Pt complex by dppf (1,1′bis(diphenylphosphino)ferrocene), compared to the inertness of the chloride ion towards the same phosphane . In another case, the indices were used to explain the different roles played by two anions in the self‐assembly of AgX with a tridentate ligand: while for X=triflate the anion is coordinated, when hexafluorophosphate is used instead, it remains as a non‐coordinated counterion . Analogous approaches have been applied by other researchers when studying substitution reactions .…”

Pseudo-2D Porous Networks via Interpenetration of 1D Zigzag Ladder-type Coordination Polymers: Adsorption and Separation of Xylene Isomers

“…Preferential adsorption of m -X over o -X (or vice versa) by means of a porous MOF is of great practical utility and importance. Among the diverse coordination frameworks, some simple 1D and 2D topological porous coordination polymers have been employed as significant prototypes for use as site-selective templates, storage sites, and small molecular containers. − Dynamic solvation/desolvation within the confined space of a porous MOF is essential to the selective adsorption process. This paper provides both (1) the structural properties of unique pseudo-2D porous coordination networks formed via interpenetration of 1D zigzag ladder-type coordination polymers and (2) a reproducible, tolerant, porous matrix for discrimination of o - and m -X.…”