二茂铁基查尔酮的理论研究和超快三阶非线性光学响应:1-二茂铁基-3-(4-溴苯基)丙烯酮
|
摘要
应用密度泛函理论计算了1-二茂铁基-3-(4-溴苯基)丙烯酮(FBPAK)的最高占据轨道(HOMO)、最低空轨道(LUMO)能量和分子极化率;采用Z-扫描技术(532nm,180fs)测定了FBPAK的三阶非线性光学参数:非线性吸收系数β=-1.0×10-12 m/W,三阶非线性分子超极化率γ=1.4×10-32esu;结果表明,FBPAK容易发生分子内电荷转移,分子容易被极化,显示出超快三阶非线性光学响应;同时测定了FBPAK的紫外吸收光谱和DSC曲线.
The highest occupied molecular orbital energy levels(HOMO),the lowest unoccupied molecular orbital energy levels(LUMO)and molecular polarizability of 1-ferrocenyl-3-(4-bromophenyl)acrylic ketone(FBPAK)have been calculated via density functional theory(DFT).Its third-order nonlinear optical(NLO)properties were measured by Z-scan technique and the resulting relevant parameters were given as following with pulse width 180 fs,laser wavelength 532 nm:β=-1.0×10-12 m/W,γ=1.4×10-32 esu;the results show that FBPAK has an intramolecular charge transfer and exhibits ultrafast third-order nonlinear optical response.The corresponding UV absorption and DSC curves were also investigated.
The highest occupied molecular orbital energy levels(HOMO),the lowest unoccupied molecular orbital energy levels(LUMO)and molecular polarizability of 1-ferrocenyl-3-(4-bromophenyl)acrylic ketone(FBPAK)have been calculated via density functional theory(DFT).Its third-order nonlinear optical(NLO)properties were measured by Z-scan technique and the resulting relevant parameters were given as following with pulse width 180 fs,laser wavelength 532 nm:β=-1.0×10-12 m/W,γ=1.4×10-32 esu;the results show that FBPAK has an intramolecular charge transfer and exhibits ultrafast third-order nonlinear optical response.The corresponding UV absorption and DSC curves were also investigated.
引文
[1]ALEN S,SAJAN D,LYNNETTE JOSEPH,et al.Synthesis,growth,vibrational spectral investigations and structure-property relationship of an organic NLO crystal:3,4-Dimethoxy chalcone[J].Chem Phys Lett,2015,636:208-215.
[2]PRABHU A N,JAYARAMA A,SUBRAHMANYA B K,et al.Growth,characterization and structural investigation of a novel nonlinear optical crystal[J].J Mol Struct,2013,1031(1):79-84.
[3]ZHAO S G,GONG P F,LUO S Y,et al.Deep-Ultraviolet transparent phosphates RbBa2(PO3)5 and Rb2Ba3(P2O7)2show nonlinear optical activity from condensation of[PO4]3-Units[J].J Am Chem Soc,2014,136(24):8560-8563.
[4]JIA J H,CUI Y H,LI Y J,et al.Synthesis,thirdorder nonlinear optical properties and theoretical analysis of vinylferrocene derivatives[J].Dyes Pigments,2013,98(2):273-279.
[5]KAUR P,KAUR M,DEPOTTER G,et al.Thermally stable ferrocenyl “push-pull”chromophores with tailorable and switchable second-order non-linear optical response:synthesis and structure-property relationship[J].J Mater Chem,2012,22(21):10597-10608.
[6]CAO Q Y,LU X,LI Z H,et al.Synthesis and characterization of ferrocenyl-acridine dyads and their multiresponse to proton and metal cations[J].J Organomet Chem,2010,695(9):1323-1327.
[7]WANG W Y,MA N N,SUN S L,et al.Redox control of ferrocene-based complexes with systematically extendedπ-conjugated connectors:switchable and tailorable second order nonlinear optics[J].Phys Chem Chem Phys,2014,16(10):4900-4910.
[8]ZOU Y,ZHANG Q,SHOWKOT HOSSAIN A M,et al.Synthesis,crystal structures,electrochemistry and nonlinear optical properties of a novel(D-A-D)biferrocenylderivative:2-Amino-4, 6-diferrocenylpyrimidine[J].J Organomet Chem,2012,720(1):66-72.
[9]WU D,XIAO L,SHI Y,et al.Novel Zn(Ⅱ)/Cd(Ⅱ)complexes based on ferrocenyl terpyridine:Crystalstructures, electrochemical and third-order nonlinear optical properties using tunable femtosecond laser[J].J Organometal Chem,2017,830(1):67-73.
[10]TEIMURI-MOFRAD R,RAHIMPOUR K,GHADARI R.Design,synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect[J].J Organometal Chem,2017,846:397-406.
[11]GODOY F,MALDONADO T,FLORES E,et al.Novel organometallic chalcones functionalized with a crown ether fragment as optical ion chemosensors[J].Appl Organometal Chem,2018,32(3):e4115.
[12]DESCHENAUX R,SERRANO E,LEVELUT A M.Ferrocene-containing liquid-crystalline dendrimers:a novel family of mesomorphic macromolecules[J].Chem Commun,1997,28(46):1577-1578.
[13]RAJ R,SAINI A,GUT J,et al.Synthesis and in vitro antiplasmodial evaluation of 7-chloroquinolinechalcone and 7-chloroquinoline-ferrocenylchalcone conjugates[J].Euro J Med Chem,2015,95(3):230-239.
[14]SHI Y F,LI Z G,FANG Y,et al.Ultrafast thirdorder nonlinear optical response of pyrene derivatives[J].Opt Laser Technol,2017,90(1):18-21.
[15]GAO J R,WANG Q,CHEN L B,et al.Synthesis and third-order optical nonlinear properties of organic polyheterocyclic materials[J].Mater Lett,2002,57(3):761-764.
[16]LI G,SONG Y L,HOU H W,et al.Synthesis,crystal structures,and third-order nonlinear optical properties of a series of ferrocenyl organometallics[J].Inorg Chem,2003,42(3):913-920.
[17]LIU Y C,KAN Y H,WU S X,et al.Theoretical study on a novel series of fullerene-containing organometall-ics Fe(η5-C55X5)2(X=CH,N,B)and their large third-order nonlinear optical properties[J].J Phys Chem A,2008,112(35):8086-8092.
[18]JOHN KIRAN A, ASHOK MITHUN,SHIVARAM HOLLA B,et al.Nonlinear optical studies of 1-3-diaryl-propenones containing 4-methylthiophenyl moieties[J].Opt Commun,2007,269(1):235-240.
[19]SEETHARAM SHETTIGAR,CHANDRASEKHARAN K,UMESH G,et al.Studies on nonlinear optical parameters of bis-chalcone derivatives doped polymer[J].Polymer,2006,47(10):3565-3567.
[20] RAVIDRA H J,JOHN KIRAN A,CHANDRASEKHARAN K,et al.Third order nonlinear optical properties and optical limiting in donor/acceptor substituted 4′-methoxy chalcone derivatives[J].Appl Phys B:Lasers Opt,2007,88(1):105-110.
[21]MULLER T J,CONRADIE J,ERASMUS E.A spectroscopic,electrochemical and DFT study of para-substituted ferrocene-containing chalcone derivatives:Structure of FcCOCHCH(p-tBuC6H4)[J].Polyhedron,2012,33(1):257-266.
[22]安辛友,吴卫东,任维义,等.Z扫描技术及其在非线性光学材料科学中的应用与进展[J].西华师范大学学报:自然科学版,2010,31(4):429-434.
[23]SUN R,YAN B L,GE J F,et al.Third-order nonlinear optical properties of unsymmetric pentamethine cyanine dyes possessing benzoxazolyl and benzothiazolyl groups[J].Dyes Pigments,2013,96(1):189-195.
[24]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09,Revision A.02,Gaussian,Inc[M].Wallingford CT,2009.
[2]PRABHU A N,JAYARAMA A,SUBRAHMANYA B K,et al.Growth,characterization and structural investigation of a novel nonlinear optical crystal[J].J Mol Struct,2013,1031(1):79-84.
[3]ZHAO S G,GONG P F,LUO S Y,et al.Deep-Ultraviolet transparent phosphates RbBa2(PO3)5 and Rb2Ba3(P2O7)2show nonlinear optical activity from condensation of[PO4]3-Units[J].J Am Chem Soc,2014,136(24):8560-8563.
[4]JIA J H,CUI Y H,LI Y J,et al.Synthesis,thirdorder nonlinear optical properties and theoretical analysis of vinylferrocene derivatives[J].Dyes Pigments,2013,98(2):273-279.
[5]KAUR P,KAUR M,DEPOTTER G,et al.Thermally stable ferrocenyl “push-pull”chromophores with tailorable and switchable second-order non-linear optical response:synthesis and structure-property relationship[J].J Mater Chem,2012,22(21):10597-10608.
[6]CAO Q Y,LU X,LI Z H,et al.Synthesis and characterization of ferrocenyl-acridine dyads and their multiresponse to proton and metal cations[J].J Organomet Chem,2010,695(9):1323-1327.
[7]WANG W Y,MA N N,SUN S L,et al.Redox control of ferrocene-based complexes with systematically extendedπ-conjugated connectors:switchable and tailorable second order nonlinear optics[J].Phys Chem Chem Phys,2014,16(10):4900-4910.
[8]ZOU Y,ZHANG Q,SHOWKOT HOSSAIN A M,et al.Synthesis,crystal structures,electrochemistry and nonlinear optical properties of a novel(D-A-D)biferrocenylderivative:2-Amino-4, 6-diferrocenylpyrimidine[J].J Organomet Chem,2012,720(1):66-72.
[9]WU D,XIAO L,SHI Y,et al.Novel Zn(Ⅱ)/Cd(Ⅱ)complexes based on ferrocenyl terpyridine:Crystalstructures, electrochemical and third-order nonlinear optical properties using tunable femtosecond laser[J].J Organometal Chem,2017,830(1):67-73.
[10]TEIMURI-MOFRAD R,RAHIMPOUR K,GHADARI R.Design,synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect[J].J Organometal Chem,2017,846:397-406.
[11]GODOY F,MALDONADO T,FLORES E,et al.Novel organometallic chalcones functionalized with a crown ether fragment as optical ion chemosensors[J].Appl Organometal Chem,2018,32(3):e4115.
[12]DESCHENAUX R,SERRANO E,LEVELUT A M.Ferrocene-containing liquid-crystalline dendrimers:a novel family of mesomorphic macromolecules[J].Chem Commun,1997,28(46):1577-1578.
[13]RAJ R,SAINI A,GUT J,et al.Synthesis and in vitro antiplasmodial evaluation of 7-chloroquinolinechalcone and 7-chloroquinoline-ferrocenylchalcone conjugates[J].Euro J Med Chem,2015,95(3):230-239.
[14]SHI Y F,LI Z G,FANG Y,et al.Ultrafast thirdorder nonlinear optical response of pyrene derivatives[J].Opt Laser Technol,2017,90(1):18-21.
[15]GAO J R,WANG Q,CHEN L B,et al.Synthesis and third-order optical nonlinear properties of organic polyheterocyclic materials[J].Mater Lett,2002,57(3):761-764.
[16]LI G,SONG Y L,HOU H W,et al.Synthesis,crystal structures,and third-order nonlinear optical properties of a series of ferrocenyl organometallics[J].Inorg Chem,2003,42(3):913-920.
[17]LIU Y C,KAN Y H,WU S X,et al.Theoretical study on a novel series of fullerene-containing organometall-ics Fe(η5-C55X5)2(X=CH,N,B)and their large third-order nonlinear optical properties[J].J Phys Chem A,2008,112(35):8086-8092.
[18]JOHN KIRAN A, ASHOK MITHUN,SHIVARAM HOLLA B,et al.Nonlinear optical studies of 1-3-diaryl-propenones containing 4-methylthiophenyl moieties[J].Opt Commun,2007,269(1):235-240.
[19]SEETHARAM SHETTIGAR,CHANDRASEKHARAN K,UMESH G,et al.Studies on nonlinear optical parameters of bis-chalcone derivatives doped polymer[J].Polymer,2006,47(10):3565-3567.
[20] RAVIDRA H J,JOHN KIRAN A,CHANDRASEKHARAN K,et al.Third order nonlinear optical properties and optical limiting in donor/acceptor substituted 4′-methoxy chalcone derivatives[J].Appl Phys B:Lasers Opt,2007,88(1):105-110.
[21]MULLER T J,CONRADIE J,ERASMUS E.A spectroscopic,electrochemical and DFT study of para-substituted ferrocene-containing chalcone derivatives:Structure of FcCOCHCH(p-tBuC6H4)[J].Polyhedron,2012,33(1):257-266.
[22]安辛友,吴卫东,任维义,等.Z扫描技术及其在非线性光学材料科学中的应用与进展[J].西华师范大学学报:自然科学版,2010,31(4):429-434.
[23]SUN R,YAN B L,GE J F,et al.Third-order nonlinear optical properties of unsymmetric pentamethine cyanine dyes possessing benzoxazolyl and benzothiazolyl groups[J].Dyes Pigments,2013,96(1):189-195.
[24]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09,Revision A.02,Gaussian,Inc[M].Wallingford CT,2009.