Crystal engineering of o-carboranyl alcohols: syntheses, crystal structures and thermal properties

Crystalline Inclusion Compounds of a Palladacyclic Tetraol Host Featuring o‐Carborane Units

“…Detailed analyses of host–guest intermolecular contacts (Table and Figures S2,S3) reveals that whereas the on‐guest solvent molecules are hydrogen bonded to the OH moieties of the palladacycle by O–H ··· O interactions, the in ‐ and out‐guest solvent molecules are interacting with the palladacycle through weaker C–H ··· O, and in some cases, C–H ··· H–B contacts. [11f], [13c], [13d]…”

“…The high thermal and chemical stability, hydrophobicity, acceptor character, ease of functionalization, and three‐dimensional nature of the icosahedral carborane clusters ( closo ‐C 2 B 10 H 12 ) make these new molecules valuable ligands in chemistry and materials science . These icosahedral molecules are versatile building blocks in supramolecular chemistry, capable of establishing a variety of conventional and nonconventional hydrogen bonding . The incorporation of carboranes as functional moieties in supramolecular chemistry has been a desirable goal, with the expectation that the resulting assemblies will exhibit interesting properties.…”

“…[10f], We have been particularly interested in relating the field of molecular crystal engineering with that of icosahedral carboranes. [9b], [9c], [11a], It is surprising that, taking into account the rich supramolecular chemistry and bulkiness of icosahedral carborane derivatives, crystalline lattice‐inclusion compounds have been hardly reported. [11i], Compound 1 , which is prepared in very good yield from one‐pot reactions and from readily available starting materials,[10a] is centered on an o ‐carborane core with one or two arms radiating out of one of the cluster carbons, containing a carbon that bears an alcohol and a 3‐pyridyl moiety.…”

“…[9b], [9c], [11a], It is surprising that, taking into account the rich supramolecular chemistry and bulkiness of icosahedral carborane derivatives, crystalline lattice‐inclusion compounds have been hardly reported. [11i], Compound 1 , which is prepared in very good yield from one‐pot reactions and from readily available starting materials,[10a] is centered on an o ‐carborane core with one or two arms radiating out of one of the cluster carbons, containing a carbon that bears an alcohol and a 3‐pyridyl moiety. The arrangement of the pyridyl moieties in this compound, from the single‐crystal X‐ray diffraction structural analysis,[9c] suggests that it could act as a bidentate ligand for the construction of metallacyclic structures.…”

N,O-Type Carborane-Based Materials

“…Using this methodology, a wide variety of mono substituted carboranyl methanol derivatives have been synthesized [42,43]. Following a similar procedure we [44][45][46][47][48][49] and others [50,51] have prepared an extensive series of new monosubstituted o-, m-and p-carboranylmethylalcohols bearing nitrogenated aromatic rings, by the addition of lithiocarboranes to the corresponding pyridylaldehydes (1-4, Chart 1 and Scheme 1). The addition of dilithiocarboranes to two equivalents of the corresponding aldehydes, under the same reaction conditions, provided a new series of disubstituted o-and m-carboranylmethylalcohols (5-6, Chart 1) [52,53].…”