Tailoring the properties of 3d transition metal complexes with different N-cycloalkyl-substituted tetrazoles

Abstract

The three ligands, 1-cyclopropyl-5H-tetrazole (C3tz, 1), 1-cyclobutyl-5H-tetrazole (C4tz, 2), and 1-cyclopentyl-5H-tetrazole (C5tz, 3) were synthesized and used for the design of 19 new energetic coordination compounds (ECC) based on 3d...

The Adjustability of Physicochemical Properties: Comparison of 1-Vinyl-5H-tetrazole and 1-Allyl-5H-tetrazole as Ligands in 3d Metal Energetic Coordination Compounds

“…In every case, the equatorial positions are occupied by the anionic nitrato ligands and one ligand moiety (Figure , right). This coordination geometry has already been observed for [Cu­(1-NET) 3 (NO 3 ) 2 ] and [Cu­(C 4 tz) 3 (NO 3 ) 2 ] …”

“…When cooled in liquid nitrogen, the color of [Fe­(1-ATZ) 6 ]­(ClO 4 ) 2 ( 10 ) changes from light beige into light purple (Figure S39), indicating a spin-crossover that changes the ground state from 5 T 2g to 1 A 1g . Like alkylated tetrazole ligands (MTZ, PTZ, C 3 tz, etc. ) 1-ATZ thus belongs to the compounds of the type [Fe­( R -TZ) 6 ] X 2 ( R -TZ = 1-alkyl/alkenyl-1 H -tetrazole, X = BF 4 , ClO 4 , PF 6 , CF 3 SO 3 ) as some of the most investigated spin-crossover systems .…”

“…In 54 Like the [Cu(1-ETZ) 6 ](ClO 3 ) 2 complex (CCDC 1898541), 23 the copper chlorate complex [Cu(1-VTZ) 6 ]-(ClO 3 ) 2 (15) crystallizes in the hexagonal space group R−3 with three formula units per unit cell (Figure 6). The compound's calculated density of 1.499 g cm −3 at 101 K is significantly lower than the densities observed for the corresponding perchlorate complex [Cu(1-VTZ) 6 ](ClO 4 ) 2 (7).…”

“…The calculated density of 1.842 g cm −3 at 103 K (17) and 1.774 g cm −3 at 101 K ( 18 Copper azide complex 19 crystallizes in the form of brown platelets in the orthorhombic space group Pbca with eight formula units per unit cell and shows the highest density of all investigated complexes (1.992 g cm −3 at 123 K), whereas [Cu(N 3 ) 2 (1-ATZ)] (20) crystallizes in the monoclinic space group P2 1 /c with four formula units per unit cell and a calculated density of 1.768 g cm −3 at 173 K. The molecular units of both are built up similar to copper(II) azide coordination compounds based on 1-alkyl tetrazoles. 33,49,54 It consists of one copper(II) central metal coordinated by one vinyl tetrazole ligand in the equatorial position and five azido anions (Figure 8). Overall, two different coordination modes of azido ligands are observed in the structure.…”

Preparation of multi-functional type coordination compounds: spanning the quantitative restriction of oxidizing groups

“…Therefore, the quantity and ratio of ClO 4 − and ligands are very important because they have great influence on some important parameters, such as enthalpy of formation, oxygen balance value, and density. 22–25 According to the coordination characteristics of ligands with metals and ClO 4 − , they can be divided into three types: (1) six ligands with mono-coordination sites can form coordination bonds with Cu( ii ). 26 ClO 4 − is not involved in the formation of coordination bonds and its ratio to ligands is 2 : 6 (shown in Scheme 1 path 1b).…”