Synthesis,Two‐Photon Absorption and Optical Limiting Properties of Multi‐branched Styryl Derivatives Based on 1,3,5‐Triazine

Five new multi‐branched two‐photon absorption triazine chromophores ( T1 – T5 ) with different donor strength, conjugation length, and direction of charge transfer have been designed and synthesized. The one‐photon fluorescence, fluorescence quantum yields, and two‐photon properties have been investigated. The two‐photon absorption (2PA) cross sections measured by the open aperture Z‐scan technique were determined to be 447, 854, 1023, 603, and 766 GM for T1 , T2 , T3 , T4 , and T5 , respectively. This result indicates that their 2PA cross section values (σ) increase with increasing electron‐donating strength of the end group, extending the conjugation length of the system, and introducing electron‐withdrawing perfluoroalkyl as side groups to the end donor. In addition, the σ value of T5 is also larger than that of T1 , which provides evidence that the σ value is relative to the direction of charge transfer (from the ends to the center of the molecule or from the center to the ends). Moreover, significant enhancement of the two‐photon absorption cross section was achieved by introducing a thiophene moiety to a conjugated CC bond. At the same time, the optical limiting behavior for these chromophores was studied by using a focused 800 nm laser beam with pulses of 140 fs duration. It was found that these molecules also exhibit good optical limiting properties. These initial results clearly demonstrate that multi‐branched triazine chromophores are a highly suitable class of two‐photon absorbing materials.     

Concise Synthesis and Two‐Photon‐Excited Deep‐Blue Emission of 1,8‐Diazapyrenes

Efficient violet–blue‐emitting molecules are especially useful for applications in full‐color displays, solid‐state lighting, as well as in two‐photon absorption (TPA) excited frequency‐upconverted violet–blue lasing. However, the reported violet–blue‐emitting molecules generally possess small TPA cross sections. In this work, new 1,8‐diazapyrenes derivatives 3 with blue two‐photon‐excited fluorescence emission were concisely synthesized by the coupling reaction of readily available 1,4‐naphthoquinone O,O‐diacetyl dioxime ( 1 ) with internal alkynes 2 under the [{RhCl₂Cp*}₂]–Cu(OAc)₂ (Cp*=pentamethylcyclopentadienyl ligand) bimetallic catalytic system. Elongation of the π‐conjugated length of 1,8‐diazapyrenes 3 led to the increase of TPA cross sections without the expense of a redshift of the emission wavelength, probably due to the rigid planar structure of chromophores. It is especially noteworthy that 2,3,6,7‐tetra(4‐bromophenyl)‐1,8‐diazapyrene ( 3c ) has a larger TPA cross section than those of other molecules reported so far. These experimental results are explained in terms of the effects of extension of the π‐conjugated system, intramolecular charge transfer, and reduced detuning energy.     

噻吩基卟啉衍生物的单光子和双光子吸收性质的理论研究

本文理论上研究了两个系列的噻吩基卟啉衍生物,这种衍生物在可见光区具有大的双光子吸收截面。用密度泛函理论和ZINDO-SOS方法,计算了分子的几何构型、电子结构,单光子和双光子吸收性质。结果显示噻吩单元的数目影响分子的单光子和双光子吸收性质。具有两个或三个噻吩基团的噻吩基卟啉衍生物在较大范围内具有可用于实际应用中的双光子吸收响应,这一性质有利于这类分子在光限幅中的应用。插入乙炔基有利于扩大共轭范围,增加分子的双光子吸收截面。同时,乙炔基团的加入导致了单光子和双光子波长的红移。从高透明性和相对大的非线性光学响应考虑,噻吩基卟啉衍生物是一类有应用前景的双光子吸收材料。     

Large Two‐Photon Absorption of Terpyridine‐Based Quadrupolar Derivatives: Towards their Applications in Optical Limiting and Biological Imaging

Developing organic chromophores with large two‐photon absorption (TPA) in both organic solvents and aqueous media is crucial owing to their applications in solid‐state photonic devices and biological imaging. Herein, a series of novel terpyridine‐based quadrupolar derivatives have been synthesized. The influences of electron‐donating group, type of conjugated bridge, as well as solvent polarity on the molecular TPA properties have been investigated in detail. In contrast to the case in organic solvents, bis(thienyl)‐benzothiadiazole as a rigid conjugated bridge will completely quench molecular two‐photon emission in aqueous media. However, the combination of alkylcarbazole as the donor and bis(styryl)benzene as a conjugation bridge can enlarge molecular TPA cross‐sections in both organic solvent and aqueous media. The reasonable two‐photon emission brightness for the organic nanoparticles of chromophores 3 – 5 in the aqueous media, prepared by the reprecipitation method, enables them to be used as probes for in vivo biological imaging.     

Synthesis and two‐photon absorption properties of conjugated polymers with N‐arylpyrrole as conjugated bridge and isolation moieties

Three novel conjugated polymers with N‐arylpyrrole as the conjugated bridge were designed and synthesized, which emitted strong one‐ or two‐photon excitation fluorescence in dilute tetrahydrofuran (THF) solution with high quantum yields. The maximal two‐photon absorption (TPA) cross‐sections of the polymers, measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in THF, were 752, 1114, and 1869 GM, respectively, indicating that the insertion of electron‐donating or electron‐withdrawing moieties into the polymer backbone could benefit to the increase of the TPA cross‐section. Their large TPA cross‐sections, coupled with the relatively high emission quantum yields, made these conjugated polymers attractive for practical applications, especially two‐photon excited fluorescence. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and Characterization of Two‐Photon Active Chromophores Based on Tetrathienoacene (TTA) and Dithienothiophene (DTT)

Three new donor–π–donor (D‐π‐D) tetrathienoacene (thieno[2′,3′:4,5]thieno[3,2‐b]thieno[2,3‐d]thiophene (TTA))‐cored chromophores, end‐functionalized with electron‐donating triphenylamine (TPA) groups, were developed and characterized for their two‐photon‐related properties by using both nano‐ and femtosecond laser pulses as the probing tools. TTA‐based chromophores exhibit stronger and more widely dispersed two‐photon absorption (2PA) than those of dithienothiophene (DTT)‐based congeners. As a consequence, the bithiophene‐conjugated TTA chromophore exhibits the highest maximum 2PA cross‐section value (up to 2500 GM) with good thermal stability, and thus, it is the best performing two‐photon chromophore among the studied model compounds. The bithiophene‐conjugated DTT analogue exhibits the second highest maximum two‐photon absorptivity of 1950 GM, which is nearly 7 times larger than that of previously reported DTT‐based chromophores.     

Experimental and Theoretical Studies of Quadrupolar Oligothiophene‐Cored Chromophores Containing Dimesitylboryl Moieties as π‐Accepting End‐Groups: Syntheses,Structures, Fluorescence,and One‐ and Two‐Photon Absorption

Quadrupolar oligothiophene chromophores composed of four to five thiophene rings with two terminal (E)‐dimesitylborylvinyl groups ( 4 V – 5 V ), and five thiophene rings with two terminal aryldimesitylboryl groups ( 5 B ), as well as an analogue of 5 V with a central EDOT ring ( 5 VE ), have been synthesized via Pd‐catalyzed cross‐coupling reactions in high yields (66–89 %). Crystal structures of 4 V , 5 B , bithiophene 2 V , and five thiophene‐derived intermediates are reported. Chromophores 4 V , 5 V , 5 B and 5 VE have photoluminescence quantum yields of 0.26–0.29, which are higher than those of the shorter analogues 1 V – 3 V (0.01–0.20), and short fluorescence lifetimes (0.50–1.05 ns). Two‐photon absorption (TPA) spectra have been measured for 2 V – 5 V , 5 B and 5 VE in the range 750–920 nm. The measured TPA cross‐sections for the series 2 V – 5 V increase steadily with length up to a maximum of 1930 GM. We compare the TPA properties of 2 V – 5 V with the related compounds 5 B and 5 VE , giving insight into the structure–property relationship for this class of chromophore. DFT and TD‐DFT results, including calculated TPA spectra, complement the experimental findings and contribute to their interpretation. A comparison to other related thiophene and dimesitylboryl compounds indicates that our design strategy is promising for the synthesis of efficient dyes for two‐photon‐excited fluorescence applications.     

Study of Linear and Nonlinear Optical Properties of Four Derivatives of Substituted Aryl Hydrazones of 1,8‐Naphthalimide

Four 1,8‐naphthalimide hydrazone molecules with different electron‐donating groups have been applied in the study of linear and nonlinear optical (NLO) properties. These compounds showed strong green emission in solution. Their NLO properties such as two‐photon absorption (TPA) behavior with femtosecond laser pulses ca. 800 nm and excited‐state absorption (ESA) behavior with nanosecond laser pulses at 532 nm were investigated. Compound 4 presented the largest two‐photon cross section (550 GM) among them due to two factors: the conjugated length of compound 4 is the longest and the electron‐donating ability of compound 4 is the strongest. Different from TPA behavior, compound 2 showed the best nonlinear absorption properties at 532 nm and its nonlinear absorption coefficient and third‐order nonlinear optical susceptibilities χ ⁽³⁾ were up to 1.41×10^?10 MKS and 4.65×10^?12 esu, respectively. Through the modification of the structure, the nonlinear optical properties of these compounds at different wavelengths (532 and 800 nm) were well tuned. The great broad‐band nonlinear optical properties indicate hydrazones are good candidates for organic nonlinear optical absorption materials.     

Water‐Soluble Triarylborane Chromophores for One‐ and Two‐Photon Excited Fluorescence Imaging of Mitochondria in Cells

Three water‐soluble tetracationic quadrupolar chromophores comprising two three‐coordinate boron π‐acceptor groups bridged by thiophene‐containing moieties were synthesised for biological imaging applications. Compound 3 containing the bulkier 5‐(3,5‐Me₂C₆H₂)‐2,2′‐(C₄H₂S)₂‐5′‐(3,5‐Me₂C₆H₂) bridge is stable over a long period of time, exhibits a high fluorescence quantum yield and strong one‐ and two‐photon absorption (TPA), and has a TPA cross section of 268 GM at 800 nm in water. Confocal laser scanning fluorescence microscopy studies in live cells indicated localisation of the chromophore at the mitochondria; moreover, cytotoxicity measurements proved biocompatibility. Thus, chromophore 3 has excellent potential for one‐ and two‐photon‐excited fluorescence imaging of mitochondrial function in cells.     

Highly Efficient,Conjugated‐Polymer‐Based Nano‐Photosensitizers for Selectively Targeted Two‐Photon Photodynamic Therapy and Imaging of Cancer Cells

Two‐photon photodynamic therapy (2P‐PDT) is a promising noninvasive treatment of cancers and other diseases with three‐dimensional selectivity and deep penetration. However, clinical applications of 2P‐PDT are limited by small two‐photon absorption (TPA) cross sections of traditional photosensitizers. The development of folate receptor targeted nano‐photosensitizers based on conjugated polymers is described. In these nano‐photosensitizers, poly{9,9‐bis[6′′‐(bromohexyl)fluorene‐2,7‐ylenevinylene]‐co‐alt‐1,4‐(2,5‐dicyanophenylene)}, which is a conjugated polymer with a large TPA cross section, acts as a two‐photon light‐harvesting material to significantly enhance the two‐photon properties of the doped photosensitizer tetraphenylporphyrin (TPP) through energy transfer. These nanoparticles displayed up to 1020‐fold enhancement in two‐photon excitation emission and about 870‐fold enhancement in the two‐photon‐induced singlet oxygen generation capability of TPP. Surface‐functionalized folic acid groups make these nanoparticles highly selective in targeting and killing KB cancer cells over NIH/3T3 normal cells. The 2P‐PDT activity of these nanoparticles was significantly improved, potentially up to about 1000 times, as implied by the enhancement factors of two‐photon excitation emission and singlet oxygen generation. These nanoparticles could act as novel two‐photon nano‐photosensitizers with combined advantages of low dark cytotoxicity, targeted 2P‐PDT with high selectivity, and simultaneous two‐photon fluorescence imaging capability; these are all required for ideal two‐photon photosensitizers.     

Theoretical Studies on the One‐ and Two‐Photon Absorption Properties of Double‐bis(styryl)benzene Derivatives

Two series of bis(styryl)benzene derivatives (BSBD), namely the single‐BSBD and the double‐BSBD, were investigated. The equilibrium geometries and electronic structures were obtained by using the density functional theory B3LYP and 6‐31G basis set. In succession, the one‐ and two‐photon absorption properties of all the molecules were studied theoretically with a ZINDO‐SOS (sum‐over‐states) method in detail. It can be seen that the double‐BSBDs have larger two‐photon absorption (TPA) cross sections in the visible‐IR range than the corresponding single‐BSBDs, demonstrating that increasing the molecular dimension is a very effective method to enhance the values of the TPA cross sections. On the other hand, it can be also noticed that the values of the TPA cross sections are correlative with the ability of donating (accepting) electrons of the terminal substituent groups R [N(CH₃)₂, CH₃, H and CF₃] in these molecules. That is, the intramolecular charge transfer is also a factor for the enhancement of the TPA efficiency. To sum up, the idea of increasing the molecular dimension to enhance the TPA cross section value is a helpful direction to explore better TPA materials for practical applications. And the double‐BSBD molecules are promising TPA materials for the further investigation from the standpoint of the high transparency and the larger TPA cross sections.     

Impact of the Synergistic Collaboration of Oligothiophene Bridges and Ruthenium Complexes on the Optical Properties of Dumbbell‐Shaped Compounds

The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the ³π? π* state of the conjugated bridge below the ³MLCT‐emitting states of the end‐capping Ru^II complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10^?78 cm⁶ s² at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications.     

Solution‐Processed Bulk‐Heterojunction Photovoltaic Cells Based on Dendritic and Star‐Shaped D‐π‐A Organic Dyes

A series of D ‐π‐A organic dendritic and star‐shaped molecules based on three various chromophores (i.e., the truxene nodes, triphenylamine moieties as the donor, and benzothiadiazole chromophore as the acceptor) and their corresponding model compounds are facilely developed. Their photophysical and electrochemical properties are investigated in detail by UV/Vis absorption and photoluminescent spectroscopy, and cyclic voltammetry. By changing the various conjugated spacers (i.e., single bond, double bond, and triple bond) among the three chromophores of dendritic series, their photophysical properties (that is, the one‐photon absorption range and two‐photon absorption cross‐section values) are effectively modulated. All D ‐π‐A conjugated oligomers show a broad and strong absorption band from 250 to 700 nm in thin films. Solution‐processed bulk‐heterojunction photovoltaic devices using our oligomer as donor and PCBM as acceptor are fabricated and measured. The power conversion efficiency of the devices based on our oligomers continuously increases from DBTTr to TRTD2A as a result of an increasing relative absorption intensity in longer wavelength region by changing the donor‐acceptor ratio and conjugated spacers between the donor and acceptor. The power conversion efficiency of the devices based on TRTD2A was 0.54 % under the illumination of AM 1.5 and 100 mW cm^?2, which is the highest value recorded based on D ‐π‐A conjugated oligomers containing triphenylamine moieties and benzothiadiazole chromophores with truxene to date.     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

Fluorene‐Based π‐Conjugated Oligomers for Efficient Three‐Photon Excited Photoluminescence and Lasing

A novel series of diphenylamino‐ and 1,2,4‐triazole‐end‐capped, fluorene‐based, π‐conjugated oligomers that includes extended oligofluorenes and oligothienylfluorenes has been synthesized by means of the palladium‐catalyzed Suzuki cross‐coupling of 9,9‐dibutyl‐7‐(diphenylamino)‐2‐fluorenylboronic acid and the corresponding 1,2,4,‐triazole‐based aryl halide as a key step. It was demonstrated that efficient two‐ and three‐photon excited photoluminescence and lasing in the blue region are obtained by pumping near‐infrared femtosecond lasers on these materials. Although the absorption and emission maxima of the highly fluorescent and extended oligofluorenes reach a saturation limit, there exists an effective conjugation length for an optimum three‐photon absorption cross section in the homologous oligofluorene series. On the other hand, the multiphoton excited emission spectrum and lasing wavelength can easily be modified or tuned by an incorporation of thienyl unit(s) into the fluorene‐based π‐conjugated core with which exceptionally large three‐photon absorption cross sections up to 3.59×10^?77 cm⁶ s² in the femtosecond regime have been obtained, thereby highlighting the potential of this series of photonic materials. The optimized full width at half‐maximum of the cavityless three‐photon upconverted blue lasing spectra are sharply narrowed to approximately 6 nm with an efficiency of up to 0.013 %.     

Synthesis,one‐ and two‐photon properties of poly[9,10‐bis(3,4‐bis(2‐ethylhexyl‐oxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐/2,7‐carbazolevinylene]

The synthesis, one‐ and two‐photon absorption (TPA) and emission properties of two novel 2,6‐anthracenevinylene‐based copolymers, poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐carbazolevinyl‐ene] ( P1 ) and poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinyl‐ene‐alt‐N‐octyl‐2,7‐carbazolevinylene] ( P2 ) were reported. The as‐synthesized polymers have the number‐average molecular weights of 1.56 × 10⁴ for P1 and 1.85 × 10⁴ g mol^?1 for P2 and are readily soluble in common organic solvents. They emit strong bluish‐green one‐ and two‐photon excitation fluorescence in dilute toluene solution (? _P1 = 0.85, ? _P2 = 0.78, λ_em( P1 ) = 491 nm, λ_em( P2 ) = 483 nm). The maximal TPA cross‐sections of P1 and P2 measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in toluene are 840 and 490 GM per repeating unit, respectively, which are obviously larger than that (210 GM) of poly[9,10‐bis‐(3,4‐bis(2‐ethylhexyloxy) phenyl)‐2,6‐anthracenevinylene], indicating that the poly(2,6‐anthracenevinylene) derivatives with large TPA cross‐sections can be obtained by inserting electron‐donating moieties into the polymer backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 463–470, 2010     

First‐principles simulations of two photon absorption spectra of dynamic structural chromophores in green fluorescent protein

The bridge photoisomerization of the chromophores of fluorescent proteins has been suggested as the possible mechanism of radiationless decay in fluorescent proteins. It indicates that this internal structure changing of chromophores great influence the optical properties of fluorescent proteins. The two‐photon absorption (TPA) properties of fluorescent proteins might also be influenced by the bridge photoisomerization of the chromophores. In this work, we simulate the dynamic conformations through rotating the bridge bond of chromophore of green fluorescent protein, and employ the time dependent density functional theory combining with the sum‐over‐states method to study their TPA characters. With our study, we find that the TPA characters of chromophore will be improved through controlling rotation of the bridge bond of chromophore. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Synthesis,One‐ and Two‐Photon Photophysical and Excited‐State Properties,and Sensing Application of a New Phosphorescent Dinuclear Cationic Iridium(III) Complex

A new phosphorescent dinuclear cationic iridium(III) complex ( Ir1 ) with a donor–acceptor–π‐bridge–acceptor–donor (D? A? π? A? D)‐conjugated oligomer ( L1 ) as a N^N ligand and a triarylboron compound as a C^N ligand has been synthesized. The photophysical and excited‐state properties of Ir1 and L1 were investigated by UV/Vis absorption spectroscopy, photoluminescence spectroscopy, and molecular‐orbital calculations, and they were compared with those of the mononuclear iridium(III) complex [Ir(Bpq)₂(bpy)]⁺PF₆^? ( Ir0 ). Compared with Ir0 , complex Ir1 shows a more‐intense optical‐absorption capability, especially in the visible‐light region. For example, complex Ir1 shows an intense absorption band that is centered at λ=448 nm with a molar extinction coefficient (ε) of about 10⁴, which is rarely observed for iridium(III) complexes. Complex Ir1 displays highly efficient orange–red phosphorescent emission with an emission wavelength of 606 nm and a quantum efficiency of 0.13 at room temperature. We also investigated the two‐photon‐absorption properties of complexes Ir0 , Ir1 , and L1 . The free ligand ( L1 ) has a relatively small two‐photon absorption cross‐section (δ_max=195 GM), but, when complexed with iridium(III) to afford dinuclear complex Ir1 , it exhibits a higher two‐photon‐absorption cross‐section than ligand L1 in the near‐infrared region and an intense two‐photon‐excited phosphorescent emission. The maximum two‐photon‐absorption cross‐section of Ir1 is 481 GM, which is also significantly larger than that of Ir0 . In addition, because the strong B? F interaction between the dimesitylboryl groups and F^? ions interrupts the extended π‐conjugation, complex Ir1 can be used as an excellent one‐ and two‐photon‐excited “ON–OFF” phosphorescent probe for F^? ions.     

The Synthesis and One‐ and Two‐Photon Optical Properties of Dipolar,Quadrupolar and Octupolar Donor–Acceptor Molecules Containing Dimesitylboryl Groups

Two series of related donor–acceptor conjugated dipolar, pseudo‐quadrupolar (V‐shaped) and octupolar molecular systems based on the p‐dimesitylborylphenylethynylaniline core, namely, 4‐(4‐dimesitylborylphenylethynyl)‐N,N‐dimethylaniline, 4‐[4‐(4‐dimesitylborylphenylethynyl)phenylethynyl]‐N,N‐dimethylaniline, 3,6‐bis(4‐dimesitylborylphenylethynyl)‐N‐n‐butylcarbazole and tris[4‐(4‐dimesitylborylphenylethynyl)phenyl]amine, and on the E‐p‐dimesitylborylethenylaniline motif, namely, E‐4‐dimesitylborylethenyl‐N,N‐di(4‐tolyl)aniline, 3,6‐bis(E‐dimesitylborylethenyl)‐N‐n‐butylcarbazole and tris(E‐4‐dimesitylborylethenylphenyl)amine have been synthesised by palladium‐catalyzed cross‐coupling and hydroboration routes, respectively. Their absorption and emission maxima, fluorescence lifetimes and quantum yields have been obtained and their two‐photon absorption (TPA) spectra and TPA cross‐sections have been examined. Of these systems, the octupolar compound tris(E‐4‐dimesitylborylethenylphenyl)amine has been shown to exhibit the largest TPA cross‐section among the two series of approximately 1000 GM at 740 nm. Its TPA performance is comparable to those of other triphenylamine‐based octupoles of similar size. The combination of such large TPA cross‐sections and high emission quantum yields, up to 0.94, make these systems attractive for applications involving two‐photon excited fluorescence (TPEF).     

Donor/Acceptor Effects on the Linear and Nonlinear Optical Properties of Geminal Diethynylethenes (g‐DEEs)

A series of geminal diethynylethenes (g‐DEEs) with electron‐donating and/or electron‐accepting (D/A) groups were synthesized via a Pd‐catalyzed cross‐coupling sequence. The UV/VIS spectra for donor–acceptor (D–A) functionalized g‐DEEs 5, 8 , and 11 show distinctive absorption trends attributable to intramolecular charge‐transfer (ICT). The bond‐length‐alternation (BLA) index for the cross‐conjugated enediyne framework varies slightly with different terminal substituents as determined by density‐functional theory (DFT) calculations and single‐crystal X‐ray analysis. Ultrafast third‐order optical nonlinearities for the g‐DEEs were measured by the differential optical Kerr effect (DOKE) technique and show that terminal donor–acceptor substitution of g‐DEEs enhances molecular second hyperpolarizabilities (γ) in comparison to donor or acceptor g‐DEEs. A small increase in the two‐photon‐absorption cross‐section (σ⁽²⁾) is observed in the series 9 – 11 as a result of increased functionalization. The effects of donor/acceptor substitution on electron delocalization along the cross‐conjugated enediyne structure are evaluated on the basis of natural‐bond‐orbital (NBO) analysis. Solid‐state structures of the four derivatives 3b, 4b, 7 and 8 were characterized by single‐crystal X‐ray structural analysis and show an asymmetric unit cell for one derivative, D–A g‐DEE 8 .