TY - JOUR

T1 - Low dimensional solids based on Mo6 cluster cyanides and Mn2+, Mn3+ or Cd2+ metal ions

T2 - Crystal chemistry, magnetic and optical properties

AU - Daigre, Gilles

AU - Lemoine, Pierric

AU - Pham, Thi Diep

AU - Demange, Valérie

AU - Gautier, Régis

AU - Naumov, Nikolay G.

AU - Ledneva, Alexandra

AU - Amela-Cortes, Maria

AU - Dumait, Noée

AU - Audebrand, Nathalie

AU - Cordier, Stéphane

N1 - Publisher Copyright: © The Royal Society of Chemistry 2018.

PY - 2018/6/28

Y1 - 2018/6/28

N2 - Five new cluster compounds based on [Mo6Bri 8(CN)a 6]2- and [Mo6Bri 6Qi 2(CN)a 6]n- (Q = S, Se, n = 3, 4) cluster units have been synthesized and characterized. Structures were determined by X-ray single crystal diffraction techniques and measurements of relevant magnetic susceptibility and optical properties were carried out. [trans-Mn(H2O)2][Mo6Br8(CN)6] (1) crystallizes in the orthorhombic system (Imma space group) and contains 2D square-net-layers built-up from [Mo6Bri 8(CN)a 6]2- and [trans-M(H2O)2]2+ moieties. Csx[trans-(MnII xMnIII 1-x)(H2O)2][Mo6Br6Q2(CN)6] (Q = S (2) and Se (3)) crystallize in the Imma space group as well; their structures are strongly related to that of 1 with a 2D square net of cluster units and transition metals. They are based on [Mo6Bri 6Qi 2(CN)a 6]3- (Q = S, Se) cluster units whose charge is counter balanced by Cs+ as well as Mn2+ and Mn3+ in high spin states. It is evidenced that the x content of the Cs+ counter-cation is equal to that of Mn2+ in order to maintain-along with (1 - x) Mn3+-23 valence electrons per cluster and a 3- charge for the cluster unit. The two oxidation states Mn2+ and Mn3+ were confirmed by electron energy loss spectroscopy (EELS) measurements. (H3O)H[cis-Cd(H2O)2][Mo6Br6Q2(CN)6]-H2O (Q = S (4) and Se (5)) crystallize in the trigonal system (P3121 space group) and are based on [Mo6Bri 6Qi 2(CN)a 6]4- (Q = S, Se) cluster units. In contrast to compounds 1-3, owing to the cis-position of the two water molecules around the transition metal, 4 and 5 exhibit a close-packed 3D structure based on an interpenetrated framework of cluster-based chains. In particular, it contains infinite chains alternating [Mo6Bri 6Qi 2(CN)a 6]4- and H+ protons as linkers. Magnetic and optical properties are also reported as well as theoretical calculations to support the structural analysis and physical properties. Structural analogies with [Re6Qi 8(CN)a 6]4- based compounds are discussed.

AB - Five new cluster compounds based on [Mo6Bri 8(CN)a 6]2- and [Mo6Bri 6Qi 2(CN)a 6]n- (Q = S, Se, n = 3, 4) cluster units have been synthesized and characterized. Structures were determined by X-ray single crystal diffraction techniques and measurements of relevant magnetic susceptibility and optical properties were carried out. [trans-Mn(H2O)2][Mo6Br8(CN)6] (1) crystallizes in the orthorhombic system (Imma space group) and contains 2D square-net-layers built-up from [Mo6Bri 8(CN)a 6]2- and [trans-M(H2O)2]2+ moieties. Csx[trans-(MnII xMnIII 1-x)(H2O)2][Mo6Br6Q2(CN)6] (Q = S (2) and Se (3)) crystallize in the Imma space group as well; their structures are strongly related to that of 1 with a 2D square net of cluster units and transition metals. They are based on [Mo6Bri 6Qi 2(CN)a 6]3- (Q = S, Se) cluster units whose charge is counter balanced by Cs+ as well as Mn2+ and Mn3+ in high spin states. It is evidenced that the x content of the Cs+ counter-cation is equal to that of Mn2+ in order to maintain-along with (1 - x) Mn3+-23 valence electrons per cluster and a 3- charge for the cluster unit. The two oxidation states Mn2+ and Mn3+ were confirmed by electron energy loss spectroscopy (EELS) measurements. (H3O)H[cis-Cd(H2O)2][Mo6Br6Q2(CN)6]-H2O (Q = S (4) and Se (5)) crystallize in the trigonal system (P3121 space group) and are based on [Mo6Bri 6Qi 2(CN)a 6]4- (Q = S, Se) cluster units. In contrast to compounds 1-3, owing to the cis-position of the two water molecules around the transition metal, 4 and 5 exhibit a close-packed 3D structure based on an interpenetrated framework of cluster-based chains. In particular, it contains infinite chains alternating [Mo6Bri 6Qi 2(CN)a 6]4- and H+ protons as linkers. Magnetic and optical properties are also reported as well as theoretical calculations to support the structural analysis and physical properties. Structural analogies with [Re6Qi 8(CN)a 6]4- based compounds are discussed.

KW - 3-DIMENSIONAL COORDINATION POLYMERS

KW - HYBRID LIQUID-CRYSTALS

KW - PRUSSIAN BLUE

KW - HEXANUCLEAR MOLYBDENUM

KW - OCTAHEDRAL CLUSTERS

KW - FRAMEWORK

KW - RHENIUM

KW - UNITS

KW - BR

KW - COMPLEXES

UR - http://www.scopus.com/inward/record.url?scp=85048884075&partnerID=8YFLogxK

U2 - 10.1039/c8ce00113h

DO - 10.1039/c8ce00113h

M3 - Article

AN - SCOPUS:85048884075

VL - 20

SP - 3396

EP - 3408

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 24

ER -