Ultrafast nonlinear absorption with multiple transformations and transient dynamics of gold nanobipyramids.

The process and condition of saturable absorption (SA) and reverse saturable absorption (RSA) of ultrafast nonlinear optics in metal nanoparticles are essential for applications including light generation, amplification, modulation, and switching. Here, we first discover and explore the multiple transformations (SA-RSA-SA) of ultrafast nonlinear absorption behavior of metal nanoparticles in femtosecond pulses. Correspondingly, the energy level model and fitting formula of multiple transformations are established to illustrate the process of optical response. The femtosecond transient absorption spectra provide information about their ultrafast dynamics process and vibrational mode, which further reveals the multiple transformation mechanisms of nonlinear absorption in gold nanobipyramids (Au-NBPs). Furthermore, Au-NBPs exhibit a significantly higher SA modulation depth up to 42% in the femtosecond, which is much higher than the reported values of other nanomaterials. Our results indicate that Au-NBPs can be used as broadband ultrafast Q-switching and mode-locking, and the conversion offers new opportunities for metal nanostructures in applications of optical switching.

Enhanced Ultrafast Broadband Reverse Saturable Absorption in Twistacenes with Enlarged π-Conjugated Central Bridge.

Optical nonlinearities of two all-carbon twistacenes, DPyA and DPyN, with the different π-conjugated central bridges were investigated. The nonlinear absorption properties of these compounds were measured using the femtosecond Z-scan with wavelengths between 650 and 900 nm. It has been found that the nonlinear absorption originated from two-photon absorption (TPA) and TPA-induced excited state absorption (ESA), wherein DPyA demonstrates higher performance than DPyN. The TPA cross section of DPyA (4300 GM) is nearly 4.3 times larger than that of DPyN at 650 nm. Moreover, the different central structures modulate the intensity of ESA at 532 nm, and DPyA exhibits an excellent ESA at 532 nm with multi-pulse excitation. Meanwhile, the result of data fitting and quantum chemistry calculation shows that the enhancement of nonlinear absorption in DPyA is due to the extended π- conjugated bridge and improved delocalization of π-electrons. These all-carbon twistacenes could yield potential applications in optical power limiting (OPL) technology.

Enhancement of Two-Photon Absorption in Boron-Dipyrromethene (BODIPY) Derivatives.

The linear and nonlinear optical properties of two BODIPY derivatives, 1,7-Diphenyl-3,5-bis(9,9-dimethyl-9H-fluoren-2-yl)-boron-diuoride-azadipyrromethene (ZL-61) and 1,7-Diphenyl-3,5-bis(4-(1,2,2-triphenylvinyl)phenyl)-boron-diuoride-azadipyrromethene (ZL-22), were comprehensively investigated based on experimental and theoretical studies. It was found that both compounds show a strong two-photon absorption response in the near-infrared regime, and the two-photon-absorption cross-section values of ZL-61 and ZL-22 were determined to be 8321 GM and 1864 GM at 800 nm, respectively. The improvement of the two-photon absorption cross section in ZL-61 was attributed to the enhancement of the donor group, which was confirmed by transient absorption measurements and DFT calculation. Our results indicate that these BODIPY derivatives are a promising candidate for optical limiting and two-photon imaging applications.

D-π-A type conjugated indandione derivatives: ultrafast broadband nonlinear absorption responses and transient dynamics.

The ultrafast nonlinear optical response of two 1,3-indandione derivatives (INB3 and INT3) was systematically investigated by the femtosecond Z-scan and pump-probe technique at multiple visible and near infrared wavelengths. Both compounds show strong broadband nonlinear absorption (NLA) and different wavelength-dependent two-photon absorption (TPA) characteristics in the range of 650-1100 nm. The TPA cross section of trithiophene-based compound INT3 was found to be larger than that of triphenylamine-based compound INB3 in the red region (650-800 nm), which is attributed to its longer π-conjugated structure and better molecular planarity. Interestingly, the effective NLA of INB3 was found to be larger than INT3 in the NIR region (800-1100 nm), which is related to the excited state absorption (ESA) induced by TPA. The ultrafast dynamics of both compounds were investigated by femtosecond transient absorption spectroscopy, which revealed a broadband ESA including several relaxation processes. This work extends nonlinear optical research on indandione derivatives, and the results suggest that these derivatives are promising candidates for optical limiting applications.

Correction: D-π-A type conjugated indandione derivatives: ultrafast broadband nonlinear absorption responses and transient dynamics.

[This corrects the article DOI: 10.1039/D2RA00349J.].

An investigation of broadband optical nonlinear absorption and transient nonlinear refraction in a fluorenone-based compound.

A novel fluorenone derivative, FO52, is designed and synthesized. The fluorenone group is introduced to provide the central π-conjugated system in the molecule and triphenylamine is substituted at both sides. Intramolecular Charge Transfer (ICT) from the terminal groups to the molecular center is confirmed via DFT calculations. Ultrafast optical nonlinearities are investigated via Z-scan and transient absorption spectroscopy (TAS) studies with a 190 fs laser. Reverse saturable absorption, two-photon induced excited-state absorption, and pure two-photon absorption are observed at 532 nm, 650 nm, and 800 nm, respectively. The different mechanisms at these wavelengths are discussed and interpreted with assistance from the results from TAS. Furthermore, strong excited-state refraction and ultrafast negative refraction from the bound electron response are resolved and discussed in phase object pump probe (POPP) experiments. The results suggest that the ICT-enhanced optical nonlinearities provide FO52 with strong optical limiting capabilities at visible wavelengths and ultrafast refraction with tiny attenuation in the near infrared region. The combination of these properties in one compound could be attractive for applications like laser protection and low-loss all-optical switching.

Tuning Nonlinear Optical Behavior by Incorporation of the Chalcogenophene into Twistacenes.

Four chalcogenophene-fused acenes containing O, S, Se, or Te, respectively, were presented, and the chalcogenophene effect on linear and nonlinear optics was systematically investigated. Their excited-state absorption performance and two-photon absorption (TPA) capacity could be modulated by the incorporating chalcogen atoms. The experimental results showed that the heavy chalcogen facilitated the intersystem crossing resulting in the presence of the triplet state absorption for PyPSe and PyPTe, and the TPA capacity gradually increased with the atomic size of the chalcogens. The theoretical calculation inferred that their nonlinear optical performance was closely related to the contributions of the chalcogenophene component to heterotwistacenes in the final excited state. In addition, PyPTe was able to work under various laser pulses from femtoseconds to nanoseconds.

Synthesis, self-assembly and nonlinear optical activity of selenium-annulated perylene diimide.

A novel Se-annulated perylene diimide derivative tethered with polyhedral oligosilsesquioxane (POSS) nanoparticles (POSS-2SePDI-POSS) was designed and prepared. The introduction of selenium atoms endows POSS-2SePDI-POSS with significant fluorescence quenching but enhanced excited-state absorption. As a result, POSS-2SePDI-POSS exhibits a distinct reverse saturable absorption characteristic, suggesting its potential application in optical limiting.

Ultrafast broadband nonlinear optical properties and excited-state dynamics of two bis-chalcone derivatives.

The development of organic nonlinear optical (NLO) chromophores is vital for various fields such as two-photon biomedical imaging, optical limiting, etc. In this work, two bis-chalcone molecules 1,4-bis[3-(2,4-dimethoxyphenyl)-2-acryloyl]benzene (C1) and 4,4'-bis[3-(2,4-bimethoxy phenyl)-2-acryloyl]biphenyl (C2) were synthesized and characterized. The excited-state dynamics of these two chromophores were studied using femtosecond transient absorption (TA) measurements. And their broadband nonlinear absorption properties and optical limiting (OL) response were investigated by femtosecond open-aperture Z-scan and intensity-dependent transmittance measurements in the wavelength range from 515 nm to 800 nm, respectively. The TA results demonstrate that C2 has strong excited-state absorption behavior and longer lifetime. In addition, the nonlinear absorption response of C2 was found to be superior to that of C1 in the visible range after 500 nm, which is attributed to a two-photon-absorption induced excited-state absorption mechanism. These results indicate that the nonlinear optical response and excited-state dynamics in bis-chalcone compounds could be enhanced via intramolecular charge-transfer.

Anthracene derivatives as broadband nonlinear optical materials: nonlinear absorption and excited-state dynamics analysis.

Two anthracene derivatives, AN-1 and AN-2, with different π-bridge lengths were designed and synthesized to investigate their optical nonlinearities. The nonlinear absorption (NLA) properties of both derivatives were measured via the femtosecond Z-scan technique with the wavelength range from 532 nm to 800 nm. The reverse saturable absorption (RSA) of both compounds results from two-photon absorption induced excited-state absorption (TPA-ESA). At all wavelengths, the reverse saturable absorption of AN-2 is superior to that of AN-1 due to a better molecular planarity for AN-2. Compared with the results of AN-1, the two-photon absorption coefficient of AN-2 can be increased by nearly 8 times (from 0.182 × 10-2 cm GW-1 for AN-1 to 1.42 × 10-2 cm GW-1 for AN-2) at 600 nm by extending the π-bridge. The evolution of femtosecond transient absorption (TA) spectra reveals the relaxation process from the singlet local excited-state (LES) to charge transfer state (CTS) for both compounds. The results imply that anthracene derivatives may be potential candidates for applications in future laser photonics.

Morphology-dependent third-order optical nonlinearity of a 2D Co-based metal-organic framework with a porphyrinic skeleton.

A two-dimensional (2D) Co-based metal-organic framework (MOF) with porphyrinic skeleton forms crystalline plates, flower-shaped clusters, and ultrathin films under optimized conditions, including the use of polyvinylpyrrolidone (PVP) as a surfactant. Ultrathin films demonstrate the best solution-based third-order nonlinear optical properties, featuring a nonlinear transmittance (T) value of 0.54, absorption coefficient (α2) of 9.5 × 10-10 m W-1 and second hyperpolarizability (γ) value of 1.37 × 10-28 esu, which are slightly better than those of the flower-shaped clusters (T = 0.65, α2 = 7.0 × 10-10 m W-1; γ = 1.27 × 10-28 esu), but marginally better than those of the crystalline thin plates (T = 0.94, α2 = 2.4 × 10-10 m W-1; γ = 0.24 × 10-28 esu).

Polyhedral oligosilsesquioxane tethered perylene diimide for application in optical limiting and rapid detection of fluoride ions.

A novel perylene diimide derivative equipped with polyhedral oligosilsesquioxane nanocages (POSS-AMPDI) was designed and synthesized for application in optical limiting. Moreover, due to the dual mechanisms of POSS collapse and intermolecular proton transfer, POSS-AMPDI exhibits high sensitivity and rapid selectivity to fluoride ions, with a detection limit as low as 1.64 × 10-8 M.

Rectangle and [2]catenane from cluster modular construction.

Reaction of [Et4N][Tp*WS3] (1) with [Cu(MeCN)4]PF6, CsCl, isonicotinic acid and CuCN, and treatment of [Et4N][Tp*WS3(CuCl)3] (2)/[Et4N][{Tp*WS3Cu3Cl}2(µ-Cl)2(µ4-Cl)] (3) with AgOTf and bpp (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate; bpp = 1,3-di(4-pyridyl)propane) give rise to [Et4N]2[{Tp*WS3Cu3(CN)0.5}2(µ-Cl)2(µ4-Cl)]2(PF6)2 (4) and [(Tp*WS3Cu3)2(µ3-Cl)2(bpp)3]2(OTf)4 (5), respectively. Compounds 4 and 5 feature cluster-based rectangle and [2]catenane architecture, and both exhibit enhanced third-order nonlinear optical responses relative to those of 1.