Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

Sukhendu Mandal; Arthur C. Reber; Meichun Qian; Ran Liu; Hector M. Saavedra; Saikat Sen; Paul S. Weiss; Shiv N. Khanna; Ayusman Sen

doi:10.1039/c2dt31286g

Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

Sukhendu Mandal, Arthur C. Reber, Meichun Qian, Ran Liu, Hector M. Saavedra, Saikat Sen, Paul S. Weiss, Shiv N. Khanna, Ayusman Sen

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

We have synthesized a series of cluster assembled materials in which the building blocks are As ₇ ^3- clusters linked by group 12 metals, Zn, Cd and Hg, to investigate the effect of covalent linkers on the band gap energy. The synthesized assemblies include zero dimensional assemblies of [Zn(As ₇) ₂] ^4-, [Cd(As ₇) ₂] ^4-, [Hg ₂(As ₇) ₂] ^4-, and [HgAsAs ₁₄] ^3- in which the clusters are separated by cryptated counterions, and assemblies in which [Zn(As ₇) ₂] ^4-, [Cd(As ₇) ₂] ^4- are linked by free alkali atoms into unusual three-dimensional structures. These covalently linked cluster-assembled materials have been characterized by elemental analysis, EDX and single-crystal X-ray diffraction. The crystal structure analysis revealed that in the case of Zn and Cd, the two As ₇ ^3- units are linked by the metal ion, while in the case of Hg, two As ₇ ^3- units are linked by either Hg-Hg or Hg-As dimers. Optical measurements indicate that the band gap energy ranges from 1.62 eV to 2.21 eV. A theoretical description based on cluster orbital theory is used to provide a microscopic understanding of the electronic character of the composite building blocks and the observed variations in the band gap energy.

Original language	English (US)
Pages (from-to)	12365-12377
Number of pages	13
Journal	Dalton Transactions
Volume	41
Issue number	40
DOIs	https://doi.org/10.1039/c2dt31286g
State	Published - Oct 28 2012

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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title = "Synthesis, structure and band gap energy of covalently linked cluster-assembled materials",

abstract = "We have synthesized a series of cluster assembled materials in which the building blocks are As 7 3- clusters linked by group 12 metals, Zn, Cd and Hg, to investigate the effect of covalent linkers on the band gap energy. The synthesized assemblies include zero dimensional assemblies of [Zn(As 7) 2] 4-, [Cd(As 7) 2] 4-, [Hg 2(As 7) 2] 4-, and [HgAsAs 14] 3- in which the clusters are separated by cryptated counterions, and assemblies in which [Zn(As 7) 2] 4-, [Cd(As 7) 2] 4- are linked by free alkali atoms into unusual three-dimensional structures. These covalently linked cluster-assembled materials have been characterized by elemental analysis, EDX and single-crystal X-ray diffraction. The crystal structure analysis revealed that in the case of Zn and Cd, the two As 7 3- units are linked by the metal ion, while in the case of Hg, two As 7 3- units are linked by either Hg-Hg or Hg-As dimers. Optical measurements indicate that the band gap energy ranges from 1.62 eV to 2.21 eV. A theoretical description based on cluster orbital theory is used to provide a microscopic understanding of the electronic character of the composite building blocks and the observed variations in the band gap energy.",

author = "Sukhendu Mandal and Reber, {Arthur C.} and Meichun Qian and Ran Liu and Saavedra, {Hector M.} and Saikat Sen and Weiss, {Paul S.} and Khanna, {Shiv N.} and Ayusman Sen",

year = "2012",

month = oct,

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doi = "10.1039/c2dt31286g",

language = "English (US)",

volume = "41",

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T1 - Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

AU - Mandal, Sukhendu

AU - Reber, Arthur C.

AU - Qian, Meichun

AU - Liu, Ran

AU - Saavedra, Hector M.

AU - Sen, Saikat

AU - Weiss, Paul S.

AU - Khanna, Shiv N.

AU - Sen, Ayusman

PY - 2012/10/28

Y1 - 2012/10/28

N2 - We have synthesized a series of cluster assembled materials in which the building blocks are As 7 3- clusters linked by group 12 metals, Zn, Cd and Hg, to investigate the effect of covalent linkers on the band gap energy. The synthesized assemblies include zero dimensional assemblies of [Zn(As 7) 2] 4-, [Cd(As 7) 2] 4-, [Hg 2(As 7) 2] 4-, and [HgAsAs 14] 3- in which the clusters are separated by cryptated counterions, and assemblies in which [Zn(As 7) 2] 4-, [Cd(As 7) 2] 4- are linked by free alkali atoms into unusual three-dimensional structures. These covalently linked cluster-assembled materials have been characterized by elemental analysis, EDX and single-crystal X-ray diffraction. The crystal structure analysis revealed that in the case of Zn and Cd, the two As 7 3- units are linked by the metal ion, while in the case of Hg, two As 7 3- units are linked by either Hg-Hg or Hg-As dimers. Optical measurements indicate that the band gap energy ranges from 1.62 eV to 2.21 eV. A theoretical description based on cluster orbital theory is used to provide a microscopic understanding of the electronic character of the composite building blocks and the observed variations in the band gap energy.

AB - We have synthesized a series of cluster assembled materials in which the building blocks are As 7 3- clusters linked by group 12 metals, Zn, Cd and Hg, to investigate the effect of covalent linkers on the band gap energy. The synthesized assemblies include zero dimensional assemblies of [Zn(As 7) 2] 4-, [Cd(As 7) 2] 4-, [Hg 2(As 7) 2] 4-, and [HgAsAs 14] 3- in which the clusters are separated by cryptated counterions, and assemblies in which [Zn(As 7) 2] 4-, [Cd(As 7) 2] 4- are linked by free alkali atoms into unusual three-dimensional structures. These covalently linked cluster-assembled materials have been characterized by elemental analysis, EDX and single-crystal X-ray diffraction. The crystal structure analysis revealed that in the case of Zn and Cd, the two As 7 3- units are linked by the metal ion, while in the case of Hg, two As 7 3- units are linked by either Hg-Hg or Hg-As dimers. Optical measurements indicate that the band gap energy ranges from 1.62 eV to 2.21 eV. A theoretical description based on cluster orbital theory is used to provide a microscopic understanding of the electronic character of the composite building blocks and the observed variations in the band gap energy.

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Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

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