Mixed-metal cluster chemistry. 30.1 syntheses and optical limiting properties of cluster-containing oligo - and polyurethanes

Michael D. Randles; Nigel T. Lucas; Marie P. Cifuentes; Mark G. Humphrey; Matthew K. Smith; Anthony C. Willis; Marek Samoc

doi:10.1021/ma0710582

Mixed-metal cluster chemistry. 30.¹ syntheses and optical limiting properties of cluster-containing oligo - and polyurethanes

Michael D. Randles, Nigel T. Lucas, Marie P. Cifuentes, Mark G. Humphrey^*, Matthew K. Smith, Anthony C. Willis, Marek Samoc

^*Corresponding author for this work

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Abstract

Molybdenum - iridium clusters Mo₂Ir₂{μ ₄-η²-C₂[(CH₂) ₆OH]₂}(μ-CO)₄(CO)₄(η-C ₅H₄R)₂ [R = H (5), Me (6), (CH ₂)₉O(THP) (7); THP = tetrahydropyranyl] are formed from reaction of Mo₂Ir₂(μ-CO)₃(CO) ₇(η-C₅H₄R)₂ with the alkyne HO(CH₂)₆C₂(CH₂)₆OH. Reaction of 6 and 7 with the diisocyanate OCN(CH₂)₄NCO affords oligourethanes [ - O(CH₂)₆(μ₄- η₂-C₂){Mo₂Ir₂(μ-CO) ₄(CO)₄(η-C₅H₄R) ₂}(CH₂)₆OC(O)NH(CH₂) ₄NHC(O) - ]_n [R = Me (12), (CH₂) ₉O(THP) (13)], with transition metal clusters in the backbone, the extent of polymerization being ascertained by size exclusion chromatography and ¹H NMR spectroscopy. Characterization of the cluster-containing oligo - and polyurethanes was aided by ¹H NMR and IR spectral comparison with model cluster diurethanes Mo₂Ir₂{μ₄- η²-C₂[(CH₂)₆OC(O)NH(CH ₂)₃Me]₂}(μ-CO)₄(CO) ₄(η-C₅H₄R)₂ [R = H (8), Me (9), (CH₂)₉O(THP) (11)], prepared from reaction between the cluster diols 5, 6, and 7 and the isocyanate Me(CH₂)₃NCO. The diol cluster 5 and cluster diurethane 8 have been characterized by single-crystal X-ray diffraction studies. Removal of the THP groups in 13 gives [ - O(CH₂)₆(μ₄-η₂-C ₂){Mo₂Ir₂(μ-CO)₄(CO) ₄(η-C₅H₄(CH₂) ₉OH)₂}(CH₂)₆OC(O)NH(CH ₂)₄NHC(O) - ]_n (14), which has been cross-linked on reaction with OCN(CH₂)₄NCO. The cluster content of the polyurethanes can be diluted; polymerization of 1:19 6:1,6-hexanediol and OCN(CH₂)₄NCO affords copolymer [ - O(CH₂)₆(μ₄-η₂-C ₂){Mo₂Ir₂(μ-CO)₄(CO) ₄(η-C₅H₄Me)₂}(CH ₂)₆OC(O)NH(CH₂)₄NHC(O){O(CH ₂)₆OC(O)NH(CH₂)₄NHC(O)}_m - ]_n (16). The optical limiting properties of these dimolybdenum-diiridium clusters and clustercontaining polymers, and related molybdenum-triiridium clusters and tungsten-containing homologues, have been assessed by open-aperture Z-scan studies at 527 nm employing ns pulses. Optical limiting merit increases upon increasing group 6 metal content, and replacing the 4d metal molybdenum with the 5d metal tungsten. Some insight into the mechanism by which these clusters function as optical limiters has been gleaned from complementary pump-probe studies, with their behavior consistent with a fast nonlinear absorption process followed by reverse saturable absorption involving metastable excited states of greater than nanosecond lifetime.

Original language	English
Pages (from-to)	7807-7818
Number of pages	12
Journal	Macromolecules
Volume	40
Issue number	22
DOIs	https://doi.org/10.1021/ma0710582
Publication status	Published - 30 Oct 2007

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@article{159b2dddfd5f4531b84a8ebb3b26d2a6,

title = "Mixed-metal cluster chemistry. 30.1 syntheses and optical limiting properties of cluster-containing oligo - and polyurethanes",

abstract = "Molybdenum - iridium clusters Mo2Ir2{μ 4-η2-C2[(CH2) 6OH]2}(μ-CO)4(CO)4(η-C 5H4R)2 [R = H (5), Me (6), (CH 2)9O(THP) (7); THP = tetrahydropyranyl] are formed from reaction of Mo2Ir2(μ-CO)3(CO) 7(η-C5H4R)2 with the alkyne HO(CH2)6C2(CH2)6OH. Reaction of 6 and 7 with the diisocyanate OCN(CH2)4NCO affords oligourethanes [ - O(CH2)6(μ4- η2-C2){Mo2Ir2(μ-CO) 4(CO)4(η-C5H4R) 2}(CH2)6OC(O)NH(CH2) 4NHC(O) - ]n [R = Me (12), (CH2) 9O(THP) (13)], with transition metal clusters in the backbone, the extent of polymerization being ascertained by size exclusion chromatography and 1H NMR spectroscopy. Characterization of the cluster-containing oligo - and polyurethanes was aided by 1H NMR and IR spectral comparison with model cluster diurethanes Mo2Ir2{μ4- η2-C2[(CH2)6OC(O)NH(CH 2)3Me]2}(μ-CO)4(CO) 4(η-C5H4R)2 [R = H (8), Me (9), (CH2)9O(THP) (11)], prepared from reaction between the cluster diols 5, 6, and 7 and the isocyanate Me(CH2)3NCO. The diol cluster 5 and cluster diurethane 8 have been characterized by single-crystal X-ray diffraction studies. Removal of the THP groups in 13 gives [ - O(CH2)6(μ4-η2-C 2){Mo2Ir2(μ-CO)4(CO) 4(η-C5H4(CH2) 9OH)2}(CH2)6OC(O)NH(CH 2)4NHC(O) - ]n (14), which has been cross-linked on reaction with OCN(CH2)4NCO. The cluster content of the polyurethanes can be diluted; polymerization of 1:19 6:1,6-hexanediol and OCN(CH2)4NCO affords copolymer [ - O(CH2)6(μ4-η2-C 2){Mo2Ir2(μ-CO)4(CO) 4(η-C5H4Me)2}(CH 2)6OC(O)NH(CH2)4NHC(O){O(CH 2)6OC(O)NH(CH2)4NHC(O)}m - ]n (16). The optical limiting properties of these dimolybdenum-diiridium clusters and clustercontaining polymers, and related molybdenum-triiridium clusters and tungsten-containing homologues, have been assessed by open-aperture Z-scan studies at 527 nm employing ns pulses. Optical limiting merit increases upon increasing group 6 metal content, and replacing the 4d metal molybdenum with the 5d metal tungsten. Some insight into the mechanism by which these clusters function as optical limiters has been gleaned from complementary pump-probe studies, with their behavior consistent with a fast nonlinear absorption process followed by reverse saturable absorption involving metastable excited states of greater than nanosecond lifetime.",

author = "Randles, {Michael D.} and Lucas, {Nigel T.} and Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Smith, {Matthew K.} and Willis, {Anthony C.} and Marek Samoc",

year = "2007",

month = oct,

day = "30",

doi = "10.1021/ma0710582",

language = "English",

volume = "40",

pages = "7807--7818",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Mixed-metal cluster chemistry. 30.1 syntheses and optical limiting properties of cluster-containing oligo - and polyurethanes

AU - Randles, Michael D.

AU - Lucas, Nigel T.

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Smith, Matthew K.

AU - Willis, Anthony C.

AU - Samoc, Marek

PY - 2007/10/30

Y1 - 2007/10/30

N2 - Molybdenum - iridium clusters Mo2Ir2{μ 4-η2-C2[(CH2) 6OH]2}(μ-CO)4(CO)4(η-C 5H4R)2 [R = H (5), Me (6), (CH 2)9O(THP) (7); THP = tetrahydropyranyl] are formed from reaction of Mo2Ir2(μ-CO)3(CO) 7(η-C5H4R)2 with the alkyne HO(CH2)6C2(CH2)6OH. Reaction of 6 and 7 with the diisocyanate OCN(CH2)4NCO affords oligourethanes [ - O(CH2)6(μ4- η2-C2){Mo2Ir2(μ-CO) 4(CO)4(η-C5H4R) 2}(CH2)6OC(O)NH(CH2) 4NHC(O) - ]n [R = Me (12), (CH2) 9O(THP) (13)], with transition metal clusters in the backbone, the extent of polymerization being ascertained by size exclusion chromatography and 1H NMR spectroscopy. Characterization of the cluster-containing oligo - and polyurethanes was aided by 1H NMR and IR spectral comparison with model cluster diurethanes Mo2Ir2{μ4- η2-C2[(CH2)6OC(O)NH(CH 2)3Me]2}(μ-CO)4(CO) 4(η-C5H4R)2 [R = H (8), Me (9), (CH2)9O(THP) (11)], prepared from reaction between the cluster diols 5, 6, and 7 and the isocyanate Me(CH2)3NCO. The diol cluster 5 and cluster diurethane 8 have been characterized by single-crystal X-ray diffraction studies. Removal of the THP groups in 13 gives [ - O(CH2)6(μ4-η2-C 2){Mo2Ir2(μ-CO)4(CO) 4(η-C5H4(CH2) 9OH)2}(CH2)6OC(O)NH(CH 2)4NHC(O) - ]n (14), which has been cross-linked on reaction with OCN(CH2)4NCO. The cluster content of the polyurethanes can be diluted; polymerization of 1:19 6:1,6-hexanediol and OCN(CH2)4NCO affords copolymer [ - O(CH2)6(μ4-η2-C 2){Mo2Ir2(μ-CO)4(CO) 4(η-C5H4Me)2}(CH 2)6OC(O)NH(CH2)4NHC(O){O(CH 2)6OC(O)NH(CH2)4NHC(O)}m - ]n (16). The optical limiting properties of these dimolybdenum-diiridium clusters and clustercontaining polymers, and related molybdenum-triiridium clusters and tungsten-containing homologues, have been assessed by open-aperture Z-scan studies at 527 nm employing ns pulses. Optical limiting merit increases upon increasing group 6 metal content, and replacing the 4d metal molybdenum with the 5d metal tungsten. Some insight into the mechanism by which these clusters function as optical limiters has been gleaned from complementary pump-probe studies, with their behavior consistent with a fast nonlinear absorption process followed by reverse saturable absorption involving metastable excited states of greater than nanosecond lifetime.

AB - Molybdenum - iridium clusters Mo2Ir2{μ 4-η2-C2[(CH2) 6OH]2}(μ-CO)4(CO)4(η-C 5H4R)2 [R = H (5), Me (6), (CH 2)9O(THP) (7); THP = tetrahydropyranyl] are formed from reaction of Mo2Ir2(μ-CO)3(CO) 7(η-C5H4R)2 with the alkyne HO(CH2)6C2(CH2)6OH. Reaction of 6 and 7 with the diisocyanate OCN(CH2)4NCO affords oligourethanes [ - O(CH2)6(μ4- η2-C2){Mo2Ir2(μ-CO) 4(CO)4(η-C5H4R) 2}(CH2)6OC(O)NH(CH2) 4NHC(O) - ]n [R = Me (12), (CH2) 9O(THP) (13)], with transition metal clusters in the backbone, the extent of polymerization being ascertained by size exclusion chromatography and 1H NMR spectroscopy. Characterization of the cluster-containing oligo - and polyurethanes was aided by 1H NMR and IR spectral comparison with model cluster diurethanes Mo2Ir2{μ4- η2-C2[(CH2)6OC(O)NH(CH 2)3Me]2}(μ-CO)4(CO) 4(η-C5H4R)2 [R = H (8), Me (9), (CH2)9O(THP) (11)], prepared from reaction between the cluster diols 5, 6, and 7 and the isocyanate Me(CH2)3NCO. The diol cluster 5 and cluster diurethane 8 have been characterized by single-crystal X-ray diffraction studies. Removal of the THP groups in 13 gives [ - O(CH2)6(μ4-η2-C 2){Mo2Ir2(μ-CO)4(CO) 4(η-C5H4(CH2) 9OH)2}(CH2)6OC(O)NH(CH 2)4NHC(O) - ]n (14), which has been cross-linked on reaction with OCN(CH2)4NCO. The cluster content of the polyurethanes can be diluted; polymerization of 1:19 6:1,6-hexanediol and OCN(CH2)4NCO affords copolymer [ - O(CH2)6(μ4-η2-C 2){Mo2Ir2(μ-CO)4(CO) 4(η-C5H4Me)2}(CH 2)6OC(O)NH(CH2)4NHC(O){O(CH 2)6OC(O)NH(CH2)4NHC(O)}m - ]n (16). The optical limiting properties of these dimolybdenum-diiridium clusters and clustercontaining polymers, and related molybdenum-triiridium clusters and tungsten-containing homologues, have been assessed by open-aperture Z-scan studies at 527 nm employing ns pulses. Optical limiting merit increases upon increasing group 6 metal content, and replacing the 4d metal molybdenum with the 5d metal tungsten. Some insight into the mechanism by which these clusters function as optical limiters has been gleaned from complementary pump-probe studies, with their behavior consistent with a fast nonlinear absorption process followed by reverse saturable absorption involving metastable excited states of greater than nanosecond lifetime.

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U2 - 10.1021/ma0710582

DO - 10.1021/ma0710582

M3 - Article

SN - 0024-9297

VL - 40

SP - 7807

EP - 7818

JO - Macromolecules

JF - Macromolecules

IS - 22

ER -

Mixed-metal cluster chemistry. 30.¹ syntheses and optical limiting properties of cluster-containing oligo - and polyurethanes

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