Selected solid-state behaviour of three di-tert-butyl-substituted N-salicylideneaniline derivatives: temperature-induced phase transitions and chromic behaviour

The synthesis, single-crystal structures and chromic behaviour of three related Schiff bases, namely, (E)-2,4-di-tert-butyl-6-{[(4-fluoro­phen­yl)imino]­meth­yl}phenol, C21H26FNO, 1, (E)-2,4-di-tert-butyl-6-{[(4-chloro­phen­yl)imino]­meth­yl}phenol, C21H26ClNO, 2, and (E)-6-{[(4-bromo­phen­yl)imino]­meth­yl}-2,4-di-tert-butyl­phenol, C21H26BrNO, 3, are reported. Two polymorphs of 1 were obtained, which were found to have different photochromic properties. Schiff bases 2 and 3 were found to be isostructural and underwent a phase transition upon cooling which was attributed to the dynamic disorder in one of the tert-butyl groups resolving at low temperature. All of the structures were found to exist in the enol rather than the keto form based on the C—O(H) and imine C=N bond lengths, and contained an intra­molecular O—H⋯N hydrogen bond alongside weaker inter­molecular C—H⋯O contacts

(E)-4-Bromo-2-[(phenylimino)methyl]phenol: a new polymorph and thermochromism

A new polymorph of (E)-4-bromo-2-[(phenylimino)methyl]phenol, C13H10Br-NO, is reported, together with a low-temperature structure determination of thepreviously published polymorph. Both polymorphs were found to have anintramolecular O—HN hydrogen bond between the phenol OH group andthe imine N atom, forming an S (6) ring. The crystals were observed to havedifferent colours at room temperature, with the previously published polymorphbeing more orange and the new polymorph more yellow. The planarity of themolecule in the two polymorphs was found to be significantly different, withdihedral angles () between the two aromatic rings for the previously published‘orange’ polymorph of = 1.8 (2)at 120 K, while the new ‘yellow’ polymorphhad = 45.6 (1)at 150 K. It was also observed that both polymorphs displayedsome degree of thermochromism and upon cooling the ‘orange’ polymorphbecame more yellow, while the ‘yellow’ polymorph became paler upon cooling

Anion Hydrogen Bonding from a ‘Revealed’ Urea Ligand

Hydrogen bonding from a urea group to hydrogen bond acceptor anions can adopt either R_2^1 (6) or R_2^2 (8) motifs depending on the proximity of hydrogen bond acceptor atoms. However, for the sterically bulky and weaker hydrogen bond acceptor triflate anion, hydrogen bond acceptor polymorphism is observe

Novel Capsular Aggregates from Flexible Tripodal Triureas with Cs Symmetry

Tris(2‐ and 3‐ureidobenzyl)amines with Cs symmetry self‐assemble in solution forming mixtures of regioisomeric capsular aggregates, one of which is chiral and the other centrosymmetric. Under certain conditions, a predominance of the centrosymmetric regioisomer is found before equilibrium, that is, a mixture close to the statistical ratio of the two species is reached. In the solid state, there is a preference for the centrosymmetric capsules. Molecular models of both regioisomeric aggregates have been built and analyzed for comparison. Guests inside capsules formed by self‐assembly of desymmetrized tris(3‐ureidobenzyl)amines feel different magnetic environments, depending on whether they are inside a chiral or an achiral regioisomeric container. Of special significance are the experiments with a more flexible triurea endowed with an ureidopropylic arm, which self‐assembles with the same efficiency as the more rigid tris(ureidobenzyl)amines

Structural studies into the spin crossover behaviour of Fe(abpt)2(NCS)2 polymorphs B and D

The spin-crossover behaviour of [Fe(abpt)2(NCS)2] (abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) polymorphs B and D has been studied using single crystal X-ray diffraction to monitor changes in structural features. High pressure single crystal measurements on polymorph B showed that it underwent a monoclinic P21/n (Z′ = 0.5) to triclinic P-1 (Z′ = 2 × 0.5) phase transition between 11.5 and 13.5 kbar, at which point it also starts to undergo a thermally inaccessible spin crossover. In polymorph D which also crystallises in the mononclinic space group P21/n (Z′ = 2 × 0.5) one of the unique Fe centres undergoes a thermal spin transition. It also displays light-induced excited spin-state trapping (LIESST), and a structure has been obtained at 30 K through continuous irradiation with a 670 nm 5 mW CW laser. In addition high pressure single crystal measurements on polymorph D showed a stepped pressure induced spin transition. At ∼9.6 kbar one of the unique Fe centres had undergone a spin transition and by ∼15 kbar both of the unique Fe centres are shown to be essentially low spin, a situation that is thermally inaccessible. Crystallographic data were collected for both polymorphs using variable temperature or high pressure single crystal X-ray diffraction to allow changes in cell parameters, bond lengths and distortion parameters to be monitored for the spin crossover or phase transition

Phosphine-alkene ligand-mediated alkyl-alkyl and alkyl-halide elimination processes from palladium(II)

N-Diphenylphosphino-7-aza-benzobicyclo[2.2.1]hept-2-ene (2) behaves as a chelating phosphine–alkene ligand for Pd0 and PdII, promoting direct alkyl–alkyl and indirect alkyl–halide reductive elimination reactions due to the stabilisation of the resulting bis(phosphine–alkene)Pd0 complex