[M6Om(C25N4H18)n]2-(M=W, Mo; n=1, 2; m=17,18)的二阶非线性光学性质的理论研究

运用密度泛函理论(DFT)的BP86方法, 对[M6Om(C25N4H18)n]2-(M=W, Mo; n=1, 2; m=17,18)进行了几何结构优化, 其中Mo系列结构化合物优化的几何结构与实验值吻合较好. 在净电场为零的条件下, 运用DFT/LB94方法计算了体系的二阶非线性光学系数β值: 体系1和2的βvec值分别为154.4×10-30和124.8×10-30 esu. 表明它们具有较大的二阶非线性光学系数, 且Mo系列比W系列的β值大. 而体系3和4的βvec值分别为218.0×10-30和191.8×10-30 esu. 体系3和4的βvec值分别比体系1和2的大, 表明增加给体的数目有利于提高NLO响应, 但都小于它们的2倍.     

一个多酸簇合物[Cu4(PPh3)6][Mo8O26]的合成、晶体结构和非线性光学性质

本文报道了一个多酸簇合物[Cu4(PPh3)6][Mo8O26]的合成、X-射线单晶结构分析及IR、XRD表征.单品结构表明中心对称的[Mo8O26]4-是由8个共边的MoO6八面体组成.该化合物具有较好的三阶非线性光学性质,其三阶非线性吸收和折射系数分别为12.9×10-11 MKS和3.13×10-11 esu.     

Theoretical investigation on redox-switchable second-order nonlinear optical responses of push-pull Cp*CoEt2C2B4H3-expanded (metallo)porphyrins

The second-order nonlinear optical (NLO) properties of the Cp*Co(C(2)H(5))(2)C(2)B(4)H(3)-expanded (metallo)porphyrins (Cp* = C(5)Me(5)) have been investigated by using ab inito RHF and density functional theory (DFT) methods. The investigation shows that the compound with expand porphyrin possesses remarkable large molecular hyperpolarizability β(tot) value, ~414.1 × 10(-30) esu (at LC-ωPBE level), and might be an excellent second-order NLO material. From the character of charge transfer (CT) transition, it indicates that the -Cp*Co(C(2)H(5))(2)C(2)B(4)H(3) acts as an electron donor in this kind of systems. As a result of the redox behavior on expanded (metallo)porphyrin, the redox switching character of the NLO responses for the systems 2a-4a has also been studied. The results show that the β(tot) values of reduced forms are larger than that of neutral ones. Furthermore, the time-dependent DFT calculation illustrates that reduced forms have a significant difference on the CT patterns versus neutral ones. The present investigation provides insight into the comparison with DFT results on estimating first hyperpolarizability and the NLO properties of the series of push-pull compounds.     

Theoretical study on the considerable second-order nonlinear optical properties of naphthylimido-substituted hexamolybdates

The static first hyperpolarizabilities and origin of nonlinear optical (NLO) properties of [(2-methylnaphthyl)imido]hexamolybdates derivatives have been investigated by density functional theory (DFT). The [(2-methylnaphthyl)imido]hexamolybdate has considerable large first hyperpolarizability, 6.780 x 10(-30) esu, and it is larger than that of [(2,6-dimethylphenyl)arylimido]hexamolybdate due to the double aromatic rings in the naphthylimido ligand. The naphthylimido ligand acts as an electron-donor and the polyanion acts as an electron-acceptor. The substituent position on the naphthylimido is a key factor to determine the first hyperpolarizability of (naphthylimido)hexamolybdate derivatives. The derivative, which the iodine atom locates on the para nitrogen on the naphthylimido ligand, has the largest betao(o) value among the iodine-substituted derivatives. It suggests that the iodine atom is quasi linear with nitrogen and Mo, which is bonded to thenitrogen atom, could generate a large static electronic field and give the large contribution to NLO response.The introducing of electron-donors significantly enhances the first hyperpolarizabilities of (naphthylimido)hexamolybdates comparing with the electron-acceptors as the electron-donating ability is significantly enhanced when the electron-donor is attached to the naphthylimido segment. The present investigation provides important insight into NLO properties of (arylimido)molybdate derivatives.     

Lindqvist型钼酸盐修饰的碳纳米管二阶非线性光学性质的理论研究

利用密度泛函理论(DFT)方法研究了[Mo₆O₁₉]^2-修饰的单壁碳纳米管的非线性光学(NLO)性质. 结果表明, [Mo₆O₁₉]^2-修饰的单壁碳纳米管作为特殊的有机-无机杂化体系, 具有显著的二阶非线性光学响应. 通过调整[Mo₆O₁₉]^2-与纳米管之间的角度, 体系的稳定性显示出规律性的变化趋势, 且二阶NLO响应发生了变化. 对静场二阶极化率(β_vec)有主要贡献的电子跃迁特征表明, [Mo₆O₁₉]^2-与碳纳米管之间角度的改变影响了分子内的给受体特征. 当角度达到30°时, 化合物显示出最大的β_vec值, 此时杂多阴离子簇为电子受体, 而碳纳米管为电子给体. 此外, 在碳纳米管的端位连接电子给体(如氨基)可有效地增大β_vec值.     

Density functional theory study on the first hyperpolarizabilities of organoimido derivatives of hexamolybdates

The first hyperpolarizabilities and origin of nonlinear optical (NLO) properties of arylimido molybdate derivatives have been investigated by density functional theory (DFT). The molecular orbital character analysis reveals that organoimido-to-polyanion charge transfer may be responsible for the NLO properties of this kind of molybdate derivatives. The NLO study shows intra-ion charge transfer is helpful to increase the first hyperpolarizability of arylimido molybdate derivatives. The lengthening of organoimido pi-conjugation enhances the betavec value. System 4 has the largest betavec value at the static electronic field, 1.238 x 10(-27)esu. Orbital analysis shows that the degree of charge transfer between polyanion cluster and organic segment was increased when the second organoimido polyanion was introduced. The present investigation provides important insight into NLO origin and properties of polyanion arylimido molybdate derivatives.     

Prediction of second-order optical nonlinearity of trisorganotin-substituted beta-Keggin polyoxotungstate

The dipole polarizabilities, second-order polarizabilities, and origin of second-order nonlinear optical (NLO) properties of trisorganotin-substituted beta-Keggin polyoxotungstate [XW9O37(SnR)3](11-n)- (X = P, Si, Ge, R = Ph; X = Si, R = PhNO2, PhCCPh) have been investigated by using time-dependent density functional response theory. This class of organic-inorganic hybrid complexes possesses a remarkably large molecular second-order NLO response, especially for [SiW9O37(SnPhCCPh)3]7- (system 5) with the static second-order polarizability (beta(vec)) computed to be 1569.66 x 10(-30) esu. Thus, these complexes have the possibility to be excellent second-order nonlinear optical materials. Analysis of the major contributions to the beta(vec) value suggests that the charge transfer from the heteropolyanion to the organic segment along the z-axis plays the key role in the NLO response of [XW9O37(SnR)3](11-n)-. The computed beta(vec) values increase as a heavy central heteroatom changes in the order Ge > Si > P. Furthermore, nitro substitution on the aryl segment and the lengthening of organostannic pi-conjugation are more important in enhancing the optical nonlinearity, especially for the latter factor. The present investigation provides important insight into the origin of the NLO properties of trisorganotin-substituted heteropolyoxotungstate.     

Energetic of molecular interface at metal-organic heterojunction: the case of thiophenethiolate chemisorbed on Au(111)

To probe the cooperativity of charge transfer between organoimido and hexamolybdate, and enhance the second-order nonlinear optical (NLO) response of organoimido derivatives of hexamolybdates, electronic structures and second-order NLO properties of a series of charge-transfer covalently bonded organoimido derived hexamolybdate complexes with donor-(π conjugated bridge)-acceptor-(π conjugated bridge)-donor or acceptor-(π conjugated bridge)-donor-(π conjugated bridge)-acceptor structures were studied by density functional theory. Studies show that different combinations of the donor, acceptor, heterocycle, –C≡C– and –N=N– moieties, and orientation of heterocycle remarkably affect the second-order NLO responses. The complexes containing electronic acceptor matched with the direction of charge transfer possess remarkable large molecular second-order polarizabilities. Electronic transitions to crucial excited states show that x-polarized transition, contributed to the off-diagonal second-order polarizabiliy tensor (β_zxx), possesses lower excited energy compared with z-polarized transition which accounted for the diagonal second-order polarizabiliy tensor (β_zzz) and thus led to the large in-plane nonlinear anisotropy (u = β_zxx/β_zzz) value, as well as good two-dimensional (2-D) second-order NLO properties. These complexes can be used as excellent 2-D second-order NLO materials from the standpoint of both large β and u values.     

Quantum chemical study of redox-switchable second-order nonlinear optical responses of D-π-A system BNbpy and metal Pt(II) chelate complex

A second-order nonlinear optical (NLO) molecular switching with redox has been investigated in the present paper. The static first hyperpolarizabilities of 5-(BMes(2))-5'-(NPh(2))-2,2'-bipyridine (BNbpy) containing three-coordinate organoboron, Pt(II) chelate complex Pt(BNbpy)Ph(2), and their reduced forms have been calculated by density functional theory (DFT) combined with the analytic derivatives method. There is an enhancement of static first hyperpolarizabilities in the reduced form according to the calculations. That is, the β(vec) value of one-electron-reduced form is ~7 times as large as that of neutral form BNbpy; the β(vec) values of one- and two-electron-reduced forms are ~3 and ~4 times as large as that of neutral form Pt(BNbpy)Ph(2), respectively. In particular, the β(vec) value of two-electron-reduced form (3)Pt(BNbpy)Ph(2)(2-) is 1349 × 10(-30) esu, ~286 times larger than its neutral form. Moreover, the component β(z) value of the metal chelate complex Pt(BNbpy)Ph(2) is 25 × 10(-30) esu, which is ~14 times as large as that of ligand BNbpy; the corresponding F(-)/CN(-) compounds show a decrease in β(x) values compared with the case of the ligand and Pt(II) complex. Analyses of geometries, density of states (DOS), and time-dependent DFT (TDDFT) calculations reveal that the one-electron reduction promotes the molecular conjugation in the x-axis and intensifies the interaction between the metal Pt(II) and ligand and then results in an enhancement of the static first hyperpolarizability, whereas the binding of F(-)/CN(-) to the B atom turns off the p(π)-π* conjugation and has no effect on the conjugation of bipyridine, which leads to a decreasing β value in the x-axis.     

A kinetically controlled trans bifunctionalized organoimido derivative of the Lindqvist-type hexamolybdate: synthesis, spectroscopic characterization, and crystal structure of (n-Bu4N)2{trans-[Mo6O17(NAr)2]} (Ar = 2,6-dimethylphenyl)

A kinetically controlled trans bifunctionalized organoimido derivative of hexamolybdate, (n-Bu(4)N)(2){trans-[Mo(6)O(17)(NAr)(2)]} (Ar = 2,6-dimethylphenyl) 1, in which the two 2,6-dimethylphenylimido groups are bonded to hexamolybdate at the trans positions, has been successfully synthesized in ca. 60% yield under mild reaction conditions. Its trans structure has been confirmed by a single-crystal X-ray diffraction study. In the crystals, cluster anions of 1 self-assemble into a 3D netlike structure via two different kinds of C-H...O hydrogen bondings, in which 1D supramolecular rectangular channels containing tetrabutylammonium cations form along the a axis. Compound 1 has also been characterized by (1)H NMR, IR, and UV-vis spectroscopic studies. UV-vis-near-IR reflectance spectroscopy measurements reveal the compound's nature of semiconductivity with an optical energy gap of 2.55 eV.     

Polyoxomolybdenum(V/VI)-sulfite compounds: synthesis, structural, and physical studies

Reaction of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) in the mixed-solvent system H(2)O/CH(3)CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH(4))(4)[Mo(4)(VI)SO(16)] x H(2)O (1), while the same reaction in acidic aqueous solution (pH = 5) yielded (NH(4))(4)[Mo(5)(VI)S(2)O(21)] x 3H(2)O (2). Compound {(H(2)bipy)(2)[Mo(5)(VI)S(2)O(21)] x H(2)O}(x) (3) was obtained from the reaction of aqueous acidic solution of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) (pH = 2.5) and 4,4'-bipyridine (4,4'-bipy). The mixed metal/sulfite species (NH(4))(7)[Co(III)(Mo(2)(V)O(4))(NH(3))(SO(3))(6)] x 4H(2)O (4) was synthesized by reacting Na(2)Mo(VI)O(4) x 2H(2)O with CoCl(2) x 6H(2)O and (NH(4))(2)SO(3) with precise control of pH (5.3) through a redox reaction. The X-ray crystal structures of compounds 1, 2, and 4 were determined. The structure of compound 1 consists of a ring of four alternately face- and edge-sharing Mo(VI)O(6) octahedra capped by the trigonal pyramidal sulfite anion, while at the base of the Mo(4) ring is an oxo group which is asymmetrically shared by all four molybdenum atoms. Compound 3 is based on the Strandberg-type heteropolyion [Mo(5)(VI)S(2)O(21)](4-), and these coordinatively saturated clusters are joined by diprotonated 4,4'-H(2)bipy(2+) through strong hydrogen bonds. Compound 3 crystallizes in the chiral space group C2. The structure of compound 4 consists of a novel trinuclear [Co(III)Mo(2)(V)SO(3)(2-)] cluster. The chiral compound 3 exhibits nonlinear optical (NLO) and photoluminescence properties. The assignment of the sulfite bands in the IR spectrum of 4 has been carried out by density functional calculations. The cobalt in 4 is a d(6) octahedral low-spin metal atom as it was evidenced by magnetic susceptibility measurements, cw EPR, BVS, and DFT calculations. The IR and solid-state UV-vis spectra as well as the thermogravimetric analyses of compounds 1-4 are also reported.     

六棱柱型金属团簇化合物Mo2Ag4S8(dppy)4的合成与非线性光学性质

新合成了一种六棱柱型金属团簇化合物Mo2Ag4S8(dppy)4, 并用X射线单晶衍射结构分析方法测定了其晶体结构. 应用Z-scan技术研究了该金属团簇化合物在波长为532 nm的纳秒激光脉冲作用下的三阶非线性光学特性. 为了研究Mo2Ag4S8(dppy)4的非线性起源, 应用泵浦探测技术研究了该金属团簇化合物在波长为532 nm的皮秒激光脉冲作用下的光学非线性响应. 实验结果表明金属团簇化合物Mo2Ag4S8(dppy)4具有自聚焦特性和非线性吸收特性; 非线性折射率n2, 非线性吸收系数β和非线性极化率χ(3)分别为1.45×10－10 esu, 6.2×10－10 m/W及2.1×10－11 esu. 实验结果表明金属团簇化合物Mo2Ag4S8(dppy)4的光学非线性响应是非线性吸收和非线性散射共同作用的结果.     

Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution

Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).     

A DFT study on NLO response of push-pull hybrid porphyrin-polyoxometalate complexes

Density functional theory (DFT) calculations were carried out to investigate the second-order nonlinear optical (NLO) properties of a series of proposed porphyrin-polyoxometalate-based complexes related to [5-(3,5-dimethyl-4-hexamolybdate amino-phenyl-ethynyl)-15-(4-nitrophenyl-ethynyl)porphinato]zinc(II) which have donor-π conjugated bridge-acceptor (D-π-A) configurations. Our calculations show that these species possess considerably large molecular total second-order polarizability (β₀), ～2000 × 10^?30 esu. Furthermore, it can be seen that {W₆O₁₈} exhibits stronger electron-donating ability than {Mo₆O₁₈}. And two-dimensional (2D) system with A-π-D-π-A structure might be a promising candidate for NLO materials based on the large β₀ (4583.5 × 10^?30 esu) and in-plane nonlinear anisotropy.     

PREPARATION AND SECOND-ORDER OPTICAL NONLINEARITY OF NOVEL PHENOXYSILICON NETWORKS BY SOL-GEL PROCESS**

 Four phenoxysilicon networks for nonlinear optical (NLO) applications were designed and prepared by an extended sol-gel process without additional H₂O and catalyst. All poled polymer network films possess high second-order nonlinear optical coefficients (d₃₃) of 10-?～10-8 esu. The investigation of NLO temporal stability at room temperature and elevated temperature (120℃) indicated that these films exhibit high d33 stability because the orientation of the chromophores are locked in the phenoxysilicon organic/inorganic networks.     

三维超分子配合物[MoO_2(OCH_2C_5H_4N)_2]制备、晶体结构及三阶非线性光学性质

Na_2MoO_4·2H_2O和2-氯甲基吡啶在水中反应得到了超分子化合物：[MoO_2 (OCH_2C_5H_4N)_2]。其单晶结构测试表明：该化合物含有两种均为6配位的但化学 环境不同的Mo(1)和Mo(2)原子;由此两种钼原子构成的中性配合物[Mo(1)O_2 (OCH_2C_5H_4N_2)]和[Mo(2)O_2(OCH_2C_5H_4N)_2]分别通过氢键O…H-C及吡啶环 间的π-π堆积作用形成了二维的A层和B层,A层与B层之间又在层间氢键的作用下 交错形成了三维的网状固态结构。用Z-scan法在DMF溶液中测试了该化合物的三阶 非线性光学性能,发现它有强的非线性吸收(α_2 = 1.92 * 10~(-9) m·W~(-1)) ,非线性极化率X~((3)) = 1.21 * 10~(-12) esu。     

Lindqvist型多酸亚胺衍生物的理论研究及设计

多金属氧酸盐的修饰化学是近年发展起来的一个热点研究领域,其中多酸的亚胺化是一种非常有效的使多酸有机官能化的方法.有机胺能够将其π电子扩展到无机框架,产生较强的d-π相互作用,从而多金属氧酸盐有机胺衍生物和远程有机官能团可以作为构筑单元构建更为复杂的多金属氧酸盐-有机杂化材料.本文综述了作者研究小组运用密度泛函理论方法研究系列Lindqvist型多酸亚胺衍生物的稳定性、成键特征和非线性光学性质,深入探讨该类有机-无机杂化衍生物非线性光学性质的起源.     

12顶点[1-R-CB11-Me11]-碳硼烷氧化-还原过程二阶NLO效应的理论研究

采用密度泛函理论（DFT）对12顶点[1-R-CB₁₁-Me₁₁]^-碳硼烷的结构和二阶非线性光学（NLO）调节效应进行计算分析. 结果表明,C位连接的取代基R供、吸电子能力的不同以及分子发生可逆氧化-还原反应对分子构型有一定影响. 由自然键轨道（NBO）电荷和电子自旋密度分析可知,分子的氧化中心是碳硼笼,分子的氧化反应可导致碳硼笼部分给、受体特性发生改变. 氧化态分子的第一超极化率总有效值（β_tot）大于相应还原态分子,当C位取代基R为供电子基团（—NH₂）的分子时,氧化态与还原态的β_tot值变化最大. 这类分子的氧化-还原反应可以有效调节二阶NLO光学效应.     

Synthesis of Poly[（3-octanoylpyrrole-2,5-diyl）-p-（N, N-dimethylamino）benzylidene] and Its Properties by Nitrogen Ion Implantation

Introduction Nonlinearoptical(NLO)organicpolymers havereceivedincreasingattentionbecauseoftheir excellentbehaviorandthegoodprospectsoftheir applicationsinhigh-techareas,suchasoptical communication,high-densityopticalstorageand all-opticalinformationprocess.Poly(pyrrolylme- thine)isanNLOmaterialwithpromisingapplica- tions[1_3].However,itssolubilityandfilm-forming performancearepoor.Inthispaper,anovelsolu- blepoly(pyrrolylmethine),poly[(3-octanoyl-pyr- role-2,5-diyl)-p-(N,N-dimethylamino)ben…     

The roles of molecular structure and effective optical symmetry in evolving dipolar chromophoric building blocks to potent octopolar nonlinear optical chromophores

A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4'-, and 4'-positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4'-ethynyl-(2,2';6',2'-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2'-terpyridine)(2+) bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)(2)](2+) core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump-probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole-dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of nonlinear optical (NLO) multipoles with extraordinary hyperpolarizabilities. Dynamic hyperpolarizability (β(λ)) values and depolarization ratios (ρ) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (λ(inc)) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (β(HRS) values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 1280 × 10(-30) esu, ρ = 3.8; Ru(tpy)[4'-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 2100 × 10(-30) esu, ρ = 3.8) to octopolar (e.g., Ru[4,4'-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2), β(HRS) = 1040 × 10(-30) esu, ρ = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4'-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2) possessing a β(HRS) value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior β(HRS) values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.