Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes: Insights for structure/luminescence/conductivity relationships

Roy N. McDougald; Bhaskar Chilukuri; Huiping Jia; Michael R. Perez; Hassan Rabaâ; Xiaoping Wang; Vladimir N. Nesterov; Thomas R. Cundari; Bruce E. Gnade; Mohammad A. Omary

doi:10.1021/ic500808q

Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes: Insights for structure/luminescence/conductivity relationships

Roy N. McDougald
, Bhaskar Chilukuri
, Huiping Jia
, Michael R. Perez
, Hassan Rabaâ
, Xiaoping Wang
, Vladimir N. Nesterov
, Thomas R. Cundari
, Bruce E. Gnade
, Mohammad A. Omary

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

37 Scopus citations

Abstract

An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au₃(RN=COR′)₃] (R, R′ = H, Me, ⁿBu, or ^cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au₃(MeN=CO ⁿBu)₃], [Au₃(ⁿBuN=COMe) ₃], [Au₃(ⁿBuN=COⁿBu)₃], and [Au₃(^cPeN=COMe)₃] are presented. Changes in R and R′ lead to distinctive variations in solid-state stacking, luminescence spectra, and conductive properties. Solid-state emission and excitation spectra for each complex display a remarkable dependence on the solid-state packing of the cyclotrimers. The electronic structure of [Au ₃(RN=COR′)₃] was investigated via molecular and solid-state simulations. Calculations on [Au₃(HN=COH)₃] models indicate that the infinitely extended chain of eclipsed structures with equidistant Au - Au intertrimer aurophilic bonding can have lower band gaps, smaller Stokes shifts, and reduced reorganization energies (λ). The action of one cyclotrimer as a molecular nanowire is demonstrated via fabrication of an organic field effect transistor and shown to produce a p-type field effect. Hole transport for the same cyclotrimer-doped within a poly(9-vinylcarbazole) host-produced a colossal increase in current density from ∼1 to ∼1000 mA/cm². Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.

Original language	English
Pages (from-to)	7485-7499
Number of pages	15
Journal	Inorganic Chemistry
Volume	53
Issue number	14
DOIs	https://doi.org/10.1021/ic500808q
State	Published - Jul 21 2014

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McDougald, R. N., Chilukuri, B., Jia, H., Perez, M. R., Rabaâ, H., Wang, X., Nesterov, V. N., Cundari, T. R., Gnade, B. E., & Omary, M. A. (2014). Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes: Insights for structure/luminescence/conductivity relationships. Inorganic Chemistry, 53(14), 7485-7499. https://doi.org/10.1021/ic500808q

@article{15219545ec3246cbb5085a7d545d4d06,

title = "Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes: Insights for structure/luminescence/conductivity relationships",

abstract = "An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au3(RN=COR′)3] (R, R′ = H, Me, nBu, or cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN=CO nBu)3], [Au3(nBuN=COMe) 3], [Au3(nBuN=COnBu)3], and [Au3(cPeN=COMe)3] are presented. Changes in R and R′ lead to distinctive variations in solid-state stacking, luminescence spectra, and conductive properties. Solid-state emission and excitation spectra for each complex display a remarkable dependence on the solid-state packing of the cyclotrimers. The electronic structure of [Au 3(RN=COR′)3] was investigated via molecular and solid-state simulations. Calculations on [Au3(HN=COH)3] models indicate that the infinitely extended chain of eclipsed structures with equidistant Au - Au intertrimer aurophilic bonding can have lower band gaps, smaller Stokes shifts, and reduced reorganization energies (λ). The action of one cyclotrimer as a molecular nanowire is demonstrated via fabrication of an organic field effect transistor and shown to produce a p-type field effect. Hole transport for the same cyclotrimer-doped within a poly(9-vinylcarbazole) host-produced a colossal increase in current density from ∼1 to ∼1000 mA/cm2. Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.",

author = "McDougald, \{Roy N.\} and Bhaskar Chilukuri and Huiping Jia and Perez, \{Michael R.\} and Hassan Raba{\^a} and Xiaoping Wang and Nesterov, \{Vladimir N.\} and Cundari, \{Thomas R.\} and Gnade, \{Bruce E.\} and Omary, \{Mohammad A.\}",

year = "2014",

month = jul,

day = "21",

doi = "10.1021/ic500808q",

language = "English",

volume = "53",

pages = "7485--7499",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "14",

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TY - JOUR

T1 - Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes

T2 - Insights for structure/luminescence/conductivity relationships

AU - McDougald, Roy N.

AU - Chilukuri, Bhaskar

AU - Jia, Huiping

AU - Perez, Michael R.

AU - Rabaâ, Hassan

AU - Wang, Xiaoping

AU - Nesterov, Vladimir N.

AU - Cundari, Thomas R.

AU - Gnade, Bruce E.

AU - Omary, Mohammad A.

PY - 2014/7/21

Y1 - 2014/7/21

N2 - An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au3(RN=COR′)3] (R, R′ = H, Me, nBu, or cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN=CO nBu)3], [Au3(nBuN=COMe) 3], [Au3(nBuN=COnBu)3], and [Au3(cPeN=COMe)3] are presented. Changes in R and R′ lead to distinctive variations in solid-state stacking, luminescence spectra, and conductive properties. Solid-state emission and excitation spectra for each complex display a remarkable dependence on the solid-state packing of the cyclotrimers. The electronic structure of [Au 3(RN=COR′)3] was investigated via molecular and solid-state simulations. Calculations on [Au3(HN=COH)3] models indicate that the infinitely extended chain of eclipsed structures with equidistant Au - Au intertrimer aurophilic bonding can have lower band gaps, smaller Stokes shifts, and reduced reorganization energies (λ). The action of one cyclotrimer as a molecular nanowire is demonstrated via fabrication of an organic field effect transistor and shown to produce a p-type field effect. Hole transport for the same cyclotrimer-doped within a poly(9-vinylcarbazole) host-produced a colossal increase in current density from ∼1 to ∼1000 mA/cm2. Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.

AB - An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au3(RN=COR′)3] (R, R′ = H, Me, nBu, or cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN=CO nBu)3], [Au3(nBuN=COMe) 3], [Au3(nBuN=COnBu)3], and [Au3(cPeN=COMe)3] are presented. Changes in R and R′ lead to distinctive variations in solid-state stacking, luminescence spectra, and conductive properties. Solid-state emission and excitation spectra for each complex display a remarkable dependence on the solid-state packing of the cyclotrimers. The electronic structure of [Au 3(RN=COR′)3] was investigated via molecular and solid-state simulations. Calculations on [Au3(HN=COH)3] models indicate that the infinitely extended chain of eclipsed structures with equidistant Au - Au intertrimer aurophilic bonding can have lower band gaps, smaller Stokes shifts, and reduced reorganization energies (λ). The action of one cyclotrimer as a molecular nanowire is demonstrated via fabrication of an organic field effect transistor and shown to produce a p-type field effect. Hole transport for the same cyclotrimer-doped within a poly(9-vinylcarbazole) host-produced a colossal increase in current density from ∼1 to ∼1000 mA/cm2. Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.

UR - https://www.scopus.com/pages/publications/84904652134

U2 - 10.1021/ic500808q

DO - 10.1021/ic500808q

M3 - Article

AN - SCOPUS:84904652134

SN - 0020-1669

VL - 53

SP - 7485

EP - 7499

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 14

ER -

Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes: Insights for structure/luminescence/conductivity relationships

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