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 journalArticle

13 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)12365-12377
Number of pages13
JournalDalton Transactions
Volume41
Issue number40
DOIs
StatePublished - Oct 28 2012

Fingerprint

Energy gap
Alkalies
Dimers
Metal ions
Energy dispersive spectroscopy
Crystal structure
Metals
Single crystals
X ray diffraction
Atoms
Composite materials
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Mandal, Sukhendu ; Reber, Arthur C. ; Qian, Meichun ; Liu, Ran ; Saavedra, Hector M. ; Sen, Saikat ; Weiss, Paul S. ; Khanna, Shiv N. ; Sen, Ayusman. / Synthesis, structure and band gap energy of covalently linked cluster-assembled materials. In: Dalton Transactions. 2012 ; Vol. 41, No. 40. pp. 12365-12377.
@article{06ff54e3bd17408c84d8987aa906a7dd,
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 = "10",
day = "28",
doi = "10.1039/c2dt31286g",
language = "English (US)",
volume = "41",
pages = "12365--12377",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "40",

}

Mandal, S, Reber, AC, Qian, M, Liu, R, Saavedra, HM, Sen, S, Weiss, PS, Khanna, SN & Sen, A 2012, 'Synthesis, structure and band gap energy of covalently linked cluster-assembled materials', Dalton Transactions, vol. 41, no. 40, pp. 12365-12377. https://doi.org/10.1039/c2dt31286g

Synthesis, structure and band gap energy of covalently linked cluster-assembled materials. / Mandal, Sukhendu; Reber, Arthur C.; Qian, Meichun; Liu, Ran; Saavedra, Hector M.; Sen, Saikat; Weiss, Paul S.; Khanna, Shiv N.; Sen, Ayusman.

In: Dalton Transactions, Vol. 41, No. 40, 28.10.2012, p. 12365-12377.

Research output: Contribution to journalArticle

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=84866918006&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84866918006&partnerID=8YFLogxK

U2 - 10.1039/c2dt31286g

DO - 10.1039/c2dt31286g

M3 - Article

VL - 41

SP - 12365

EP - 12377

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 40

ER -

Mandal S, Reber AC, Qian M, Liu R, Saavedra HM, Sen S et al. Synthesis, structure and band gap energy of covalently linked cluster-assembled materials. Dalton Transactions. 2012 Oct 28;41(40):12365-12377. https://doi.org/10.1039/c2dt31286g