Conjugation through Si-O-Si bonds, silsesquioxane (SQ) half cage copolymers, extended examples via SiO0.5/SiO1.5 units: multiple emissive states in violation of Kasha's rule.

We previously reported that phenyl- and vinyl-silsesquioxanes (SQs), [RSiO1.5]8,10,12 (R = Ph or vinyl) functionalized with three or more conjugated moieties show red-shifted absorption- and emission features suggesting 3-D conjugation via a cage centered LUMOs. Corner missing [PhSiO1.5]7(OSiMe3)3 and edge opened, end capped [PhSiO1.5]8(OSiMe2)2 (double decker, DD) analogs also offer red shifted spectra again indicating 3-D conjugation and a cage centered LUMO. Copolymerization of DD [PhSiO1.5]8(OSiMevinyl)2 with multiple R-Ar-Br gives copolymers with emission red-shifts that change with degree of polymerization (DP), exhibit charge transfer to F4TNCQ and terpolymer averaged red-shifts suggesting through chain conjugation even with two (O-Si-O) end caps possibly via a cage centered LUMO. Surprisingly, ladder (LL) SQ, (vinylMeSiO2)[PhSiO1.5]4(O2SiMevinyl) copolymers offer emission red-shifts even greater for analogous copolymers requiring a different explanation. Here we assess the photophysical behavior of copolymers of a more extreme SQ form: the half cage [PhSiO1.5]4(OSiMe2Vinyl)4, Vy4HC SQs. We again see small red-shifted absorptions coupled with significant red-shifted emissions, even with just a half cage, thus further supporting the existence of pπ-dπ and/or σ*-π* conjugation through Si-O-Si bonds and contrary to most traditional views of Si-O-Si linked polymers. These same copolymers donate an electron to F4TCNQ generating the radical anion, F4TCNQ-. as further proof of conjugation. Column chromatographic separation of short from longer chain oligomers reveals a direct correlation between DP and emission λmax red-shifts as another indication of conjugation. Further, one- and two-photon absorption and emission spectroscopy reveals multiple excited fluorescence-emitting states in a violation of Kasha's rule wherein emission occurs only from the lowest excited state. Traditional modeling studies again find HOMO LUMO energy levels residing only on the aromatic co-monomers rather than through Si-O-Si bonds as recently found in related polymers.

Biobased Silicon and Biobased Silica: Two Production Routes Whose Time has Come.

This study offers an updated bioeconomy perspective on biobased routes to high-purity silicon and silica in the context of the societal, economic and environmental trends reshaping chemical processes. We summarize the main aspects of the green chemistry technologies capable of transforming current production methods. Coincidentally, we discuss selected industrial and economic aspects. Finally, we offer perspectives of how said technologies could/will reshape current chemical and energy production.

Stabilizing High-Voltage Cathodes via Ball-Mill Coating with Flame-Made Nanopowder Electrolytes.

LiMn1.5Ni0.5O4 (LMNO) spinel has recently been the subject of intense research as a cathode material because it is cheap, cobalt-free, and has a high discharge voltage (4.7 V). However, the decomposition of conventional liquid electrolytes on the cathode surface at this high oxidation state and the dissolution of Mn2+ have hindered its practical utility. We report here that simply ball-mill coating LMNO using flame-made nanopowder (NPs, 5-20 wt %, e.g., LiAlO2, LATSP, LLZO) electrolytes generates coated composites that mitigate these well-recognized issues. As-synthesized composite cathodes maintain a single P4332 cubic spinel phase. Transmission electron microscopy (TEM) and X-ray photoelectron spectra (XPS) show island-type NP coatings on LMNO surfaces. Different NPs show various effects on LMNO composite cathode performance compared to pristine LMNO (120 mAh g-1, 93% capacity retention after 50 cycles at C/3, ∼67 mAh g-1 at 8C, and ∼540 Wh kg-1 energy density). For example, the LMNO + 20 wt % LiAlO2 composite cathodes exhibit Li+ diffusivities improved by two orders of magnitude over pristine LMNO and discharge capacities up to ∼136 mAh g-1 after 100 cycles at C/3 (98% retention), while 10 wt % LiAlO2 shows ∼110 mAh g-1 at 10C and an average discharge energy density of ∼640 Wh kg-1. Detailed postmortem analyses on cycled composite electrodes demonstrate that NP coatings form protective layers. In addition, preliminary studies suggest potential utility in all-solid-state batteries (ASSBs).

Unconventional conjugation in macromonomers and polymers.

Multiple reviews have been written concerning conjugated macromonomers and polymers both as general descriptions and for specific applications. In most examples, conjugation occurs via electronic communication via continuous overlap of π orbitals, most often on carbon. These systems can be considered to offer traditional forms of conjugation. In this review, we attempt to survey macromonomers and polymers that offer conjugation involving novel forms of carbon and/or other elements but with conjugation achieved via other bonding formats, including many where the mechanism(s) whereby such behavior is observed remain unresolved. In particular, this review emphasizes silsesquioxane containing polymeric materials that offer properties found typically in conjugated polymers. However, conjugation in these polymers appears to occur via saturated siloxane bonds within monomeric units that make up a variety of polymer systems. Multiple photophysical analytical methods are used as a means to demonstrate conjugation in systems where traditional conjugation is not apparent.

LaTiO2N nanopowders (NPs) with low surface defect density via nitridation of flame made NPs retaining simple perovskite structure.

This work introduces a novel route to perovskite LaTiO2N nanopowders (NPs) via nitridation of perovskite LaTiO3 NPs in an NH3 gas flow at 1050 °C/NH3/15 h, in which a simple perovskite structure (ABX3) is retained during nitridation. The LaTiO3 NP is formed with a trace of a second phase in a precursor oxide NP (LTO-4/3) produced using liquid-feed flame spray pyrolysis (LF-FSP) of a metallo-organic ethanol solution with La/Ti = 4/3. The characterization of the resulting powders allows for a comparison with LaTiO2N NPs synthesized by the nitridation of the La2Ti2O7 precursor oxide NP (LTO-1) with a perovskite slab structure (A2B2X7) also prepared by LF-FSP of a La/Ti = 1 solution. Williamson-Hall plots suggest that the as-produced LaTiO2N from LTO-1 offers a quite small but effective crystallite size of 16-18 nm with almost no lattice spacing fluctuations, while LaTiO2N from LTO-4/3 presents a larger effective crystallite size of 50-52 nm with some lattice spacing fluctuations. UV-vis diffuse reflectance analysis reveals that, unlike LaTiO2N from LTO-1, the spectra of LaTiO2N from LTO-4/3 show a quite low absorption background above the wavelength of the optical absorption edge (∼580 nm), suggesting good crystallinity with a very low surface defect density. Both oxynitride NPs appear to offer utility as inorganic pigments with different colours, while LaTiO2N NPs from LTO-4/3 have advantages for various applications, including potential as a visible-light-driven water splitting photocatalyst.

Conjugated Copolymers That Shouldn't Be.

Multiple studies have explored using cage silsesquioxanes (SQs) as backbone elements in hybrid polymers motivated by their well-defined structures and physical and mechanical properties. As part of this general exploration, we report unexpected photophysical properties of copolymers derived from divinyl double decker (DD) SQs, [vinyl(Me)Si(O0.5 )2 ][PhSiO1.5 ]8 [(O0.5 )2 Si(Me)vinyl] (vinylDDvinyl). These copolymers exhibit strong emission red-shifts relative to model compounds, implying unconventional conjugation, despite vinyl(Me)Si(O-)2 siloxane bridges. In an effort to identify minimum SQ structures that do/do not offer extended conjugation, we explored Heck catalyzed co-polymerization of vinyl-ladder(LL)-vinyl compounds, vinyl(Me/Ph)Si(O0.5 )2 [PhSiO1.5 ]4 (O0.5 )2 Si(Me/Ph)vinyl, with Br-Ar-Br. Most surprising, the resulting oligomers show 30-60 nm emission red-shifts beyond those seen with vinylDDvinyl analogs despite lacking a true cage. Further evidence for unconventional conjugation includes apparent integer charge transfer (ICT) between LL-co-thiophene, bithiophene, and thienothiophene with 10 mol % F4 TCNQ, suggesting potential as p-type doped organic/inorganic semiconductors.

LiAlO2/LiAl5O8 Membranes Derived from Flame-Synthesized Nanopowders as a Potential Electrolyte and Coating Material for All-Solid-State Batteries.

Recently, γ-LiAlO2 has attracted considerable attention as a coating in Li-ion battery electrodes. However, its potential as a Li+ ceramic electrolyte is limited due to its poor ionic conductivity (<10-10 S cm-1). Here, we demonstrate an effective method of processing LiAlO2 membranes (<50 µm) using nanopowders (NPs) produced via liquid-feed flame spray pyrolysis (LF-FSP). Membranes consisting of selected mixtures of lithium aluminate polymorphs and Li contents were processed by conventional tape casting of NPs followed by thermocompression of the green films (100 °C/10 kpsi/10 min). The sintered green films (1100 °C/2 h/air) present a mixture of LiAlO2 (∼72 wt %) and LiAl5O8 (∼27 wt %) phases, offering ionic conductivities (>10-6 S cm-1) at ambient with an activation energy of 0.5 eV. This greatly increases their potential utility as ceramic electrolytes for all-solid-state batteries, which could simplify battery designs, significantly reduce costs, and increase their safety. Furthermore, a solid-state Li/Li3.1AlO2/Li symmetric cell was assembled and galvanostatically cycled at 0.375 mA cm-2 current density, exhibiting a transference number ≈ 1.

Solid Electrolytes for Li-S Batteries: Solid Solutions of Poly(ethylene oxide) with LixPON- and LixSiPON-Based Polymers.

We report here efforts to synthesize free-standing, dry polymer electrolytes that exhibit superior ionic conductivities at ambient for Li-S batteries. Co-dissolution of poly(ethylene oxide) (PEO) (Mn 900k) with LixPON and LixSiPON polymer systems at a ratio of approximately 3:2 followed by casting provides transparent, solid-solution films 25-50 µm thick, lowering PEO crystallinity, and providing measured impedance values of 0.1-2.8 × 10-3 S/cm at ambient. These values are much higher than simple PEO/Li+ salt systems. These solid-solution polymer electrolytes (PEs) are (1) thermally stable to 100 °C; (2) offer activation energies of 0.2-0.5 eV; (3) suppress dendrite formation; and (4) enable the use of lithium anodes at current densities as high as 3.5 mAh/cm2. Galvanostatic cycling of SPAN/PEs/Li cell (SPAN = sulfurized, carbonized polyacrylonitrile) shows discharge capacities of 1000 mAh/gsulfur at 0.25C and 800 mAh/gsulfur at 1C with high coulumbic efficiency over 100 cycles.

Polymer Precursor Derived LixPON Electrolytes: Toward Li-S Batteries.

Efforts to develop polymer precursor electrolytes that offer properties anticipated to be similar or superior to (lithium phosphorus oxynitride, LiPON) glasses are reported. Such precursors offer the potential to be used to process LiPON-like thin glass/ceramic coatings for use in all solid state batteries, ASBs. Here, LiPON glasses provide a design basis for the synthesis of sets of oligomers/polymers by lithiation of OP(NH2)3-x(NH)x [from OP(NH)3],OP(NH2)3-x(NHSiMe3)x and [P═N]3(NHSiMe3)6-x(NH)x. The resulting systems have degrees of polymerization of 5-20. Treatment with selected amounts of LiNH2 provides varying degrees of lithiation and Li+ conducting properties commensurate with Li+ content. Polymer electrolytes impregnated in/on Celgard exhibit Li+ conductivities up to ∼1 × 10-5S cm-1 at room temperature and are thermally stable to ∼150 °C. A Li-S battery assembled using a Li6SiPON composition polymer electrolyte exhibits an initial reversible capacity of 1500 mAh gsulfur-1 and excellent cycle performance at 0.25 and 0.5 C rate over 120 cycles at room temperature.

Ce-Substituted Nanograin Na3Zr2Si2PO12 Prepared by LF-FSP as Sodium-Ion Conductors.

The urgent need for high-performance solid electrolytes has aroused considerable focus on NASICON ceramics. Optimization of processing routes to dense, defect-free materials has yet to receive sufficient attention to date. Although traditional solid-state reaction methods followed by repetitive ball milling and sintering up to 10 h above 1200 °C are common place, the resulting average particle sizes are usually too large to produce dense, robust structures because of excessive grain growth. In this study, nanopowders (NPs) are produced, which offer a superior opportunity to make dense, high-phase-purity sintered bodies. Here, we report on the effect of sintering conditions on the microstructures and phase of Ce4+-substituted NASICON samples, Na3CexZr2-xSi2PO12 (x = 0, 0.1, 0.2, 0.3). NPs permit processing fine-grained solid-state electrolytes with 98% relative density at 1100 °C/5 h. In addition, Rietveld refinement was applied to evaluate 3-D Na-ion diffusion channels among different NASICON samples. Also, it is found that adding 5 at % Ce4+ does not change the phase structure but dramatically enlarges the Na+ diffusion "bottleneck" from 5.4 to 5.6 Å2. This may be one reason for these samples to exhibit conductivities of 2.4 × 10-2 S cm-1 at 140 °C.

Facile Approach to Recycling Highly Cross-Linked Thermoset Silicone Resins under Ambient Conditions.

Silicone resins are traditional thermoset polymers with an inorganic backbone, affording chemical inertness and high thermal stability, which also makes them inherently difficult to recycle by traditional methods. Here, we demonstrate that catalytic amounts of fluoride ion at room temperature solubilize highly cross-linked silicone resins initially cured up to 250 °C. After solubilization equilibria are achieved, solvent is removed to reform the polymer network. Coatings on aluminum substrates and monoliths of virgin and recycled silicone resins were evaluated for hydrophobicity, wear resistance, substrate adhesion, and thermal stability. Silicones recycled under optimized conditions retained nearly 100% wear resistance, thermal stability, and adhesion properties. In some instances, the recycled coatings offer properties superior to the initial materials.

In Situ Methylation Transforms Aggregation-Caused Quenching into Aggregation-Induced Emission: Functional Porous Silsesquioxane-Based Composites with Enhanced Near-Infrared Emission.

Methylation of TPA-DCM (2-(2,6-bis-4-(diphenylamino)stryryl-4H-pyranylidene)malononitrile) that exhibits aggregation-caused quenching (ACQ) results in the fluorophore M-TPA-DCM (2-(2,6-bis((E)-4-(di-p-tolylamino)-styryl)-4H-pyran-4-ylidene]malononitrile) that shows aggregation-induced emission (AIE) and NIR fluorescence and has a conjugated "D-π-A-π-D" electronic configuration. Friedel-Crafts reaction of TPA-DCM and octavinylsilsesquioxane (OVS) resulted in a family of porous materials (TPAIEs) that contain the M-TPA-DCM motif and show large Stokes shifts (180 nm), NIR emission (670 nm), tunable porosity (SBET from 160 to 720 m2 g-1 , pore volumes of 0.13-0.55 cm3 g-1 ), as well as high thermal stability (400 °C, 5 % mass loss, N2 ). As a simple test case, one of TPAIE materials was used to sense Ru3+ ions with high selectivity and sensitivity.

High Surface Area, Thermally Stable, Hydrophobic, Microporous, Rigid Gels Generated at Ambient from MeSi(OEt)3 /(EtO)3 SiCH2 CH2 Si(OEt)3 Mixtures by F- -Catalyzed Hydrolysis.

High surface area materials are of considerable interest for gas storage/capture, molecular sieving, catalyst supports, as well as for slow-release drug-delivery systems. We report here a very simple and fast route to very high surface area, mechanically robust, hydrophobic polymer gels prepared by fluoride-catalyzed hydrolysis of mixtures of MeSi(OEt)3 and bis-triethoxysilylethane (BTSE) at room temperature. These materials offer specific surface areas up to 1300 m2 g-1 , peak pore sizes of 0.8 nm and thermal stabilities above 200 °C. The gelation times and surface areas can be controlled by adjusting the solvent volume (dichloromethane), percent fluoride (as nBu4 NF or TBAF) and the BTSE contents. Polymers with other corners and linkers were also explored. These materials will further expand the materials databank for use in vacuum insulation panels and as thermally stable release and capture media.

[PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules.

Traditional electrophilic bromination follows long established "rules": electron-withdrawing substituents cause bromination selective for meta positions, whereas electron-donating substituents favor ortho and para bromination. In contrast, in the [PhSiO1.5]8,10,12 silsesquioxanes, the cages act as bulky, electron withdrawing groups equivalent to CF3; yet bromination under mild conditions, without a catalyst, greatly favors ortho substitution. Surprisingly, ICl iodination without a catalyst favors (>90%) para substitution [p-IC6H4SiO1.5]8,10,12. Finally, nitration and Friedel-Crafts acylation and sulfonylation are highly meta selective, >80%. In principle, the two halogenation formats coupled with the traditional electrophilic reactions provide selective functionalization at each position on the aromatic ring. Furthermore, halogenation serves as a starting point for the synthesis of two structural isomers of practical utility, i.e. in drug prospecting. The o-bromo and p-iodo compounds are easily modified by catalytic cross-coupling to append diverse functional groups. Thereafter, F-/H2O2 treatment cleaves the Si-C bonds replacing Si with OH. This represents a rare opportunity to introduce hydroxyl groups to aromatic rings, a process not easily accomplished using traditional organic synthesis methods. The as-produced phenol provides additional opportunities for modification. Each cage can be considered a nanoreactor generating 8-12 product molecules. Examples given include syntheses of 4,2'-R,OH-stilbenes and 4,4'-R,OH-stilbenes (R = Me, CN). Unoptimized cleavage of the Br/I derivatives yields 55-85% phenol. Unoptimized cleavage of the stilbene derivatives yields 35-40% (3-5 equivalents of phenol) in the preliminary studies presented here. In contrast, meta R-phenol yields are 80% (7-10 mol per cage).

Durable and Hydrophobic Organic-Inorganic Hybrid Coatings via Fluoride Rearrangement of Phenyl T12 Silsesquioxane and Siloxanes.

There have been many successful efforts to enhance the water shedding properties of hydrophobic and superhydrophobic coatings, but durability is often a secondary concern. Here, we describe durable and hydrophobic coatings prepared via fluoride catalyzed rearrangement reaction of dodecaphenylsilsesquioxane [PhSiO1.5]12 (DDPS) with octamethylcyclotetrasiloxane (D4). Hydrophobic properties and wear resistance are maximized by incorporating both low surface energy moieties and cross-linkable moieties into the siloxane network. Water contact angles as high as 150 ± 4° were achieved even after 150 wear cycles with SiC sandpaper (2000 grit, 2 kPa). These hybrid organic-inorganic copolymers also have high thermal stabilities after curing at 250 °C (Td5% ≥ 340 °C in air) due to the siloxane network with a maximum Td5% of >460 °C measured for the system with the highest silsesquioxane content. The coating systems presented here offer a unique combination of hydrophobicity and mechanical/thermal stability and could greatly expand the utility of water repellent coatings.

Facile synthesis, microstructure and photophysical properties of core-shell nanostructured (SiCN)/BN nanocomposites.

Increasing structural complexity at nanoscale can permit superior control over photophysical properties in the precursor-derived semiconductors. We demonstrate here the synthesis of silicon carbonitride (SiCN)/boron nitride (BN) nanocomposites via a polymer precursor route wherein the cobalt polyamine complexes used as the catalyst, exhibiting novel composite structures and photophysical properties. High Resolution Transmission Electron Microscopy (HRTEM) analysis shows that the diameters of SiCN-BN core-shell nanocomposites and BN shells are 50‒400 nm and 5‒25 nm, respectively. BN nanosheets (BNNSs) are also observed with an average sheet size of 5‒15 nm. The photophysical properties of these nanocomposites are characterized using the UV-Vis and photoluminescence (PL) analyses. The as-produced composites have emission behavior including an emission lifetime of 2.5 ns (±20 ps) longer observed in BN doped SiCN than that seen for SiC nanoparticles. Our results suggest that the SiCN/BN nanocomposites act as semiconductor displaying superior width photoluminescence at wavelengths spanning the visible to near-infrared (NIR) spectral range (400‒700 nm), owing to the heterojunction of the interface between the SiC(N) nanowire core and the BN nanosheet shell.

Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic, Green, and Sustainable Sources.

The direct depolymerization of SiO2 to distillable alkoxysilanes has been explored repeatedly without success for 85 years as an alternative to carbothermal reduction (1900 °C) to Si(met) , followed by treatment with ROH. We report herein the base-catalyzed depolymerization of SiO2 with diols to form distillable spirocyclic alkoxysilanes and Si(OEt)4. Thus, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, or ethylene glycol (EGH2) react with silica sources, such as rice hull ash, in the presence of NaOH (10%) to form H2O and distillable spirocyclic alkoxysilanes [bis(2-methyl-2,4-pentanediolato) silicate, bis(2,2,4-trimethyl-1,3-pentanediolato) silicate or Si(eg)2 polymer with 5-98% conversion, as governed by surface area/crystallinity. Si(eg)2 or bis(2-methyl-2,4-pentanediolato) silicate reacted with EtOH and catalytic acid to give Si(OEt)4 in 60% yield, thus providing inexpensive routes to high-purity precipitated or fumed silica and compounds with single Si-C bonds.

D5h [PhSiO1.5]10 synthesis via F(-) catalyzed rearrangement of [PhSiO1.5]n. An experimental/computational analysis of likely reaction pathways.

We describe here the synthesis and analysis of the reaction pathways leading to formation of the rare D5h decaphenylsilsesquioxane (SQ) [PhSiO1.5]10via F(-) catalyzed rearrangement of [PhSiO1.5]nn = 8, 12, and oligomers initially synthesized from PhSi(OEt)3. Isolated yields of ∼50% [PhSiO1.5]10 are obtained via rearrangement of all starting materials. The recovered starting materials can be re-equilibrated using catalytic F(-) to generate similar yields in second batches. These yields arise because [PhSiO1.5]10 exhibits higher solubility and better energy stabilization (10 kcal mol(-1) theory) in CH2Cl2 compared to [PhSiO1.5]8 or [PhSiO1.5]12. Reaction intermediates were identified using time dependent (19)F NMR and MALDI-ToF mass spectrometry eventually equilibrating to form the 8 : 10 : 12 cages in a 1 : 3 : 1.3 equilibrium in CH2Cl2. Experimental results coupled with modeling using the Gamess computational package provide multiple reasonable pathways for SQ rearrangements to [RSiO1.5]10, starting from [RSiO1.5]8. Heats of reaction for interconversion of the model intermediates [HSiO1.5]x determined computationally, were used to select the most reasonable reaction pathways. The findings support a mechanism involving activation and cleavage of a T8 cage corner by F(-) attachment, followed by the corners stepwise removal as [i.e. RSi(OH)3], followed thereafter by reinsertion forming [RSiO1.5]9-OH followed by, insertion of another corner to form [RSiO1.5]10-(OH)2 and finally condensation to give [RSiO1.5]10. The most enthalpically favorable path (-24 kcal mol(-1)) involves a hybrid mechanism.

Escaping the Tyranny of Carbothermal Reduction: Fumed Silica from Sustainable, Green Sources without First Having to Make SiCl4.

Fumed silica is produced in 1000 tons per year quantities by combusting SiCl4 in H2 /O2 flames. Given that both SiCl4 and combustion byproduct HCl are corrosive, toxic and polluting, this route to fumed silica requires extensive safeguards that may be obviated if an alternate route were found. Silica, including rice hull ash (RHA) can be directly depolymerized using hindered diols to generate distillable spirocyclic alkoxysilanes or Si(OEt)4 . We report here the use of liquid-feed flame spray pyrolysis (LF-FSP) to combust the aforementioned precursors to produce fumed silica very similar to SiCl4 -derived products. The resulting powders are amorphous, necked, <50 nm average particle sizes, with specific surface areas (SSAs) of 140-230 m(2) g(-1) . The LF-FSP approach does not require the containment constraints of the SiCl4 process and given that the RHA silica source is produced in million ton per year quantities worldwide, the reported approach represents a sustainable, green and potentially lower-cost alternative.

Analyzing structure-photophysical property relationships for isolated T8, T10, and T12 stilbenevinylsilsesquioxanes.

Silsesquioxanes (SQs) are of considerable interest for hybrid electronic and photonic materials. However, to date, their photophysical properties have not been studied extensively, thus their potential remains conjecture. Here we describe the first known efforts to map structure-photophysical properties as a function of cage symmetry and size by comparing identically functionalized systems. Our focus here is on the solution photophysical properties of the title stilbenevinyl-SQs, which were characterized using single photon absorption, two-photon absorption, fluorescence emission, and fluorescence lifetime kinetics. We offer here the first detailed photophysical study of the larger pure T10 and T12 silsesquioxanes and show photophysical properties that differ as a function of size, especially in their fluorescence behavior, indicating that cage size and/or symmetry can strongly affect photophysical properties. We also find that they offer excitation-dependent emission (evidence of rare "red-edge" effects). The T10 stilbenevinyl-SQ offers up to a 10-fold increase in two-photon absorption cross section per chromophore over a free chromophore, signifying increased electronic coupling. The SQ cage compounds show "rise times" of 700-1000 fs and low anisotropy (~0.1) in fluorescence lifetime kinetic studies. These results indicate excited state energy transfer, unobserved for the free chromophores and unexpected for systems with "inert" silica cores and for 3-D hybrid molecular species. These findings provide the first detailed photophysical study of chromophore-functionalized T10 and T12 silsesquioxanes and show that SQs may be considered a separate class of compounds/materials with anticipated novel properties of value in developing new components for electronic and photonic applications.