Patterned Functionalization of Gold and Single Crystal Silicon via Photochemical Reaction of Surface-Confined Derivatives of (η5-C5H5)Mn(CO)3

Doris Kang; Mark S. Wrighton

doi:10.1021/la00058a033

Patterned Functionalization of Gold and Single Crystal Silicon via Photochemical Reaction of Surface-Confined Derivatives of (η⁵-C₅H₅)Mn(CO)₃

Doris Kang
, Mark S. Wrighton

Department of Chemistry

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

26 Scopus citations

Abstract

Treatment of a single crystal Si wafer (n- or p-type, 100 face) having a thin surface SiO_x, layer with Cl₃Si(η⁵-C₅H₄)Mn(CO)₃, I, yields the Si-confined complex [Si]OSi(η⁵-C₅H₄) Mnt(CO)₃. Coverage of about a monolayer is typically achieved. Near-UV irradiation of the Si-confined tricarbonyl in PPh₂(n-octyl) (L) gives the surface-confined substitution product [Si]OSi(η⁵-C₅H₄)Mn(CO)₂L. The identities of the Si-confined complexes were determined by comparison of their IR CO stretching frequencies with those of (CH₃)₃Si(η⁵-C₅H₄)Mn(CO)₂L and of the corresponding high surface area SiO₂-confined species, [SiO₂]-OSi(CH₃)₂(η⁵-C₅H₄)Mn(CO)₂L (L = CO, PPh₂(n-octyl)). Treatment of a Au-coated Si wafer with HS-(CH₂)₁₁(η⁵-C₅H₄)Mn(CO)₃, II, yields about a monolayer of the Au-confined complex [Au]S(CH₂)n(η⁵-C₅H₄)Mn(CO)₃. Near-UV irradiation of the Au-confined tricarbonyl in the presence of PPh₂(n-octyl) (L) yields the surface-confined substitution product [Au]S(CH₂)n(η⁵-C₅H₄)Mn(CO)₂L. The photochemistries of surface-confined I and II differ from the photochemistries of the corresponding solution species. No surface-confined disubstituted species [Si]OSi(η⁵-C₅H₄)Mn(CO)L₂ or [Au]S(CH₂)₁₁(η⁵-C₅H₄)Mn(CO)L₂ are formed, although (η⁵-C₅H₄R)Mn(CO)L₂, R = -Si(CH₃)₃ or -(CH₂)₁₁SH, form readily upon irradiation of (η⁵-C₅H₄)Mn(CO)₂L in solutions containing PPh₂(n-octyl). In addition, even the formation of mono-substitution products is more difficult on a surface than in solution. The difficulty is manifested by the need for high entering ligand concentrations and the inability to achieve significant chemical yields of [Si]OSi(η⁵-C₅H₄)Mn(CO)₂L or [Au]S(CH₂)₁₁(η⁵-C₅H₄)Mn(CO)₂L with a wide range of L. This and the absence of multiple substitution products are rationalized by invoking interaction of the surface-confined molecule with the surface. Patterning of the surface of a Si wafer modified with I or of Au modified with II is readily accomplished, since photosubstitution occurs only on irradiated portions of the surface.

Original language	English
Pages (from-to)	2169-2174
Number of pages	6
Journal	Langmuir
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/la00058a033
State	Published - Oct 1 1991

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@article{d270e09d0ca14ceab5412e5e3f3705f5,

title = "Patterned Functionalization of Gold and Single Crystal Silicon via Photochemical Reaction of Surface-Confined Derivatives of (η5-C5H5)Mn(CO)3",

abstract = "Treatment of a single crystal Si wafer (n- or p-type, 100 face) having a thin surface SiOx, layer with Cl3Si(η5-C5H4)Mn(CO)3, I, yields the Si-confined complex [Si]OSi(η5-C5H4) Mnt(CO)3. Coverage of about a monolayer is typically achieved. Near-UV irradiation of the Si-confined tricarbonyl in PPh2(n-octyl) (L) gives the surface-confined substitution product [Si]OSi(η5-C5H4)Mn(CO)2L. The identities of the Si-confined complexes were determined by comparison of their IR CO stretching frequencies with those of (CH3)3Si(η5-C5H4)Mn(CO)2L and of the corresponding high surface area SiO2-confined species, [SiO2]-OSi(CH3)2(η5-C5H4)Mn(CO)2L (L = CO, PPh2(n-octyl)). Treatment of a Au-coated Si wafer with HS-(CH2)11(η5-C5H4)Mn(CO)3, II, yields about a monolayer of the Au-confined complex [Au]S(CH2)n(η5-C5H4)Mn(CO)3. Near-UV irradiation of the Au-confined tricarbonyl in the presence of PPh2(n-octyl) (L) yields the surface-confined substitution product [Au]S(CH2)n(η5-C5H4)Mn(CO)2L. The photochemistries of surface-confined I and II differ from the photochemistries of the corresponding solution species. No surface-confined disubstituted species [Si]OSi(η5-C5H4)Mn(CO)L2 or [Au]S(CH2)11(η5-C5H4)Mn(CO)L2 are formed, although (η5-C5H4R)Mn(CO)L2, R = -Si(CH3)3 or -(CH2)11SH, form readily upon irradiation of (η5-C5H4)Mn(CO)2L in solutions containing PPh2(n-octyl). In addition, even the formation of mono-substitution products is more difficult on a surface than in solution. The difficulty is manifested by the need for high entering ligand concentrations and the inability to achieve significant chemical yields of [Si]OSi(η5-C5H4)Mn(CO)2L or [Au]S(CH2)11(η5-C5H4)Mn(CO)2L with a wide range of L. This and the absence of multiple substitution products are rationalized by invoking interaction of the surface-confined molecule with the surface. Patterning of the surface of a Si wafer modified with I or of Au modified with II is readily accomplished, since photosubstitution occurs only on irradiated portions of the surface.",

author = "Doris Kang and Wrighton, \{Mark S.\}",

year = "1991",

month = oct,

day = "1",

doi = "10.1021/la00058a033",

language = "English",

volume = "7",

pages = "2169--2174",

journal = "Langmuir",

issn = "0743-7463",

number = "10",

}

TY - JOUR

T1 - Patterned Functionalization of Gold and Single Crystal Silicon via Photochemical Reaction of Surface-Confined Derivatives of (η5-C5H5)Mn(CO)3

AU - Kang, Doris

AU - Wrighton, Mark S.

PY - 1991/10/1

Y1 - 1991/10/1

N2 - Treatment of a single crystal Si wafer (n- or p-type, 100 face) having a thin surface SiOx, layer with Cl3Si(η5-C5H4)Mn(CO)3, I, yields the Si-confined complex [Si]OSi(η5-C5H4) Mnt(CO)3. Coverage of about a monolayer is typically achieved. Near-UV irradiation of the Si-confined tricarbonyl in PPh2(n-octyl) (L) gives the surface-confined substitution product [Si]OSi(η5-C5H4)Mn(CO)2L. The identities of the Si-confined complexes were determined by comparison of their IR CO stretching frequencies with those of (CH3)3Si(η5-C5H4)Mn(CO)2L and of the corresponding high surface area SiO2-confined species, [SiO2]-OSi(CH3)2(η5-C5H4)Mn(CO)2L (L = CO, PPh2(n-octyl)). Treatment of a Au-coated Si wafer with HS-(CH2)11(η5-C5H4)Mn(CO)3, II, yields about a monolayer of the Au-confined complex [Au]S(CH2)n(η5-C5H4)Mn(CO)3. Near-UV irradiation of the Au-confined tricarbonyl in the presence of PPh2(n-octyl) (L) yields the surface-confined substitution product [Au]S(CH2)n(η5-C5H4)Mn(CO)2L. The photochemistries of surface-confined I and II differ from the photochemistries of the corresponding solution species. No surface-confined disubstituted species [Si]OSi(η5-C5H4)Mn(CO)L2 or [Au]S(CH2)11(η5-C5H4)Mn(CO)L2 are formed, although (η5-C5H4R)Mn(CO)L2, R = -Si(CH3)3 or -(CH2)11SH, form readily upon irradiation of (η5-C5H4)Mn(CO)2L in solutions containing PPh2(n-octyl). In addition, even the formation of mono-substitution products is more difficult on a surface than in solution. The difficulty is manifested by the need for high entering ligand concentrations and the inability to achieve significant chemical yields of [Si]OSi(η5-C5H4)Mn(CO)2L or [Au]S(CH2)11(η5-C5H4)Mn(CO)2L with a wide range of L. This and the absence of multiple substitution products are rationalized by invoking interaction of the surface-confined molecule with the surface. Patterning of the surface of a Si wafer modified with I or of Au modified with II is readily accomplished, since photosubstitution occurs only on irradiated portions of the surface.

AB - Treatment of a single crystal Si wafer (n- or p-type, 100 face) having a thin surface SiOx, layer with Cl3Si(η5-C5H4)Mn(CO)3, I, yields the Si-confined complex [Si]OSi(η5-C5H4) Mnt(CO)3. Coverage of about a monolayer is typically achieved. Near-UV irradiation of the Si-confined tricarbonyl in PPh2(n-octyl) (L) gives the surface-confined substitution product [Si]OSi(η5-C5H4)Mn(CO)2L. The identities of the Si-confined complexes were determined by comparison of their IR CO stretching frequencies with those of (CH3)3Si(η5-C5H4)Mn(CO)2L and of the corresponding high surface area SiO2-confined species, [SiO2]-OSi(CH3)2(η5-C5H4)Mn(CO)2L (L = CO, PPh2(n-octyl)). Treatment of a Au-coated Si wafer with HS-(CH2)11(η5-C5H4)Mn(CO)3, II, yields about a monolayer of the Au-confined complex [Au]S(CH2)n(η5-C5H4)Mn(CO)3. Near-UV irradiation of the Au-confined tricarbonyl in the presence of PPh2(n-octyl) (L) yields the surface-confined substitution product [Au]S(CH2)n(η5-C5H4)Mn(CO)2L. The photochemistries of surface-confined I and II differ from the photochemistries of the corresponding solution species. No surface-confined disubstituted species [Si]OSi(η5-C5H4)Mn(CO)L2 or [Au]S(CH2)11(η5-C5H4)Mn(CO)L2 are formed, although (η5-C5H4R)Mn(CO)L2, R = -Si(CH3)3 or -(CH2)11SH, form readily upon irradiation of (η5-C5H4)Mn(CO)2L in solutions containing PPh2(n-octyl). In addition, even the formation of mono-substitution products is more difficult on a surface than in solution. The difficulty is manifested by the need for high entering ligand concentrations and the inability to achieve significant chemical yields of [Si]OSi(η5-C5H4)Mn(CO)2L or [Au]S(CH2)11(η5-C5H4)Mn(CO)2L with a wide range of L. This and the absence of multiple substitution products are rationalized by invoking interaction of the surface-confined molecule with the surface. Patterning of the surface of a Si wafer modified with I or of Au modified with II is readily accomplished, since photosubstitution occurs only on irradiated portions of the surface.

UR - https://www.scopus.com/pages/publications/0026237859

U2 - 10.1021/la00058a033

DO - 10.1021/la00058a033

M3 - Article

AN - SCOPUS:0026237859

SN - 0743-7463

VL - 7

SP - 2169

EP - 2174

JO - Langmuir

JF - Langmuir

IS - 10

ER -

Patterned Functionalization of Gold and Single Crystal Silicon via Photochemical Reaction of Surface-Confined Derivatives of (η⁵-C₅H₅)Mn(CO)₃

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