TY - JOUR
T1 - Organometallic complexes for nonlinear optics. 39.1 syntheses and third-order nonlinear optical properties of first-generation peripherally metalated arylalkynyl dendrimers
AU - Powell, Clem E.
AU - Hurst, Stephanie K.
AU - Morrall, Joseph P.
AU - Cifuentes, Marie P.
AU - Roberts, Rachel L.
AU - Samoc, Marek
AU - Humphrey, Mark G.
PY - 2007/8/27
Y1 - 2007/8/27
N2 - Steric control of the extent of reaction has been developed to rapidly synthesize ligated metal-containing dendrons that have been employed in arylalkynyl complex dendrimer synthesis. Reaction of 1,3,5-triethynylbenzene with excess cis-[RuCl2(dppe)2] affords 1,3-{trans-[(dppe)2ClRuC≡C]}2-5-HC≡CC 6H3 (1). Reaction of 1 with 4-RC6H 4C≡CH affords 1,3-{trans-[(dppe)2(RC 6H4-4-C≡C)RuC≡C]}2-5-HC≡ CC6H3 [R = H (2a), NO2 (2b), NH2 (2c)]. 2a-c are coupled with 4-Me3SiC≡CC6H 4I under Sonogashira conditions to give 1,3-{trans-[(dppe) 2(RC6H4-4-C≡C)RuC≡C]} 2-5-(Me3SiC≡CC6H4-4-C≡C) C6H3 [R = H (3a), NO2 (3b), NH2 (3c)], which can be desilylated to afford 1,3-{trans-[(dppe)2(RC 6H4-4-C≡C)-RuC=C]}2-5-(HC≡CC 6H4-4-C≡C)C6H3 [R = H (4a), NO2 (4b), NH2 (4c)]. Sonogashira coupling of 4a-c with 1,3,5-triiodobenzene gives the systematically varied peripherally metalated arylalkynyl dendrimers 1,3,5-(3,5-{trans-[(dppe)2(RC 6H4-4-C≡C)RuC≡C]}2C 6H3-1-C≡CC6H4-4-C≡C) 3C6H3 [R = H (5a), NO2 (5b), NH 2 (5c)]. All complexes show two reversible oxidation processes by cyclic voltammetry. Cubic nonlinearities determined using the Z-scan technique and low-repetition femtosecond pulses at 660 and 800 nm increase on π-system lengthening and progression from dendron to dendrimer. In contrast to all other complexes in this study, 5b is a saturable absorber at 800 nm. Dispersion of both the refractive and the absorptive nonlinearities of 5b has been determined, and the behavior has been modeled for the first time with an inorganic complex.
AB - Steric control of the extent of reaction has been developed to rapidly synthesize ligated metal-containing dendrons that have been employed in arylalkynyl complex dendrimer synthesis. Reaction of 1,3,5-triethynylbenzene with excess cis-[RuCl2(dppe)2] affords 1,3-{trans-[(dppe)2ClRuC≡C]}2-5-HC≡CC 6H3 (1). Reaction of 1 with 4-RC6H 4C≡CH affords 1,3-{trans-[(dppe)2(RC 6H4-4-C≡C)RuC≡C]}2-5-HC≡ CC6H3 [R = H (2a), NO2 (2b), NH2 (2c)]. 2a-c are coupled with 4-Me3SiC≡CC6H 4I under Sonogashira conditions to give 1,3-{trans-[(dppe) 2(RC6H4-4-C≡C)RuC≡C]} 2-5-(Me3SiC≡CC6H4-4-C≡C) C6H3 [R = H (3a), NO2 (3b), NH2 (3c)], which can be desilylated to afford 1,3-{trans-[(dppe)2(RC 6H4-4-C≡C)-RuC=C]}2-5-(HC≡CC 6H4-4-C≡C)C6H3 [R = H (4a), NO2 (4b), NH2 (4c)]. Sonogashira coupling of 4a-c with 1,3,5-triiodobenzene gives the systematically varied peripherally metalated arylalkynyl dendrimers 1,3,5-(3,5-{trans-[(dppe)2(RC 6H4-4-C≡C)RuC≡C]}2C 6H3-1-C≡CC6H4-4-C≡C) 3C6H3 [R = H (5a), NO2 (5b), NH 2 (5c)]. All complexes show two reversible oxidation processes by cyclic voltammetry. Cubic nonlinearities determined using the Z-scan technique and low-repetition femtosecond pulses at 660 and 800 nm increase on π-system lengthening and progression from dendron to dendrimer. In contrast to all other complexes in this study, 5b is a saturable absorber at 800 nm. Dispersion of both the refractive and the absorptive nonlinearities of 5b has been determined, and the behavior has been modeled for the first time with an inorganic complex.
UR - http://www.scopus.com/inward/record.url?scp=34548574862&partnerID=8YFLogxK
U2 - 10.1021/om700398n
DO - 10.1021/om700398n
M3 - Article
SN - 0276-7333
VL - 26
SP - 4456
EP - 4463
JO - Organometallics
JF - Organometallics
IS - 18
ER -