Spontaneous chiral self-assembly of CdSe@CdS nanorods

•The helical structure of [email protected] nanorods was formed with achiral reagents•The stability chiral crystal dislocation calculated•Spontaneous symmetry breaking occurred in the self-assembly nanorod Spontaneous (SCSB) inorganic compounds is a fundamental issue origin biochirality prebiotic environment. Although spontaneous formation space groups, stacking faults, and dislocations has been extensively investigated, enantiomeric excess rarely considered for inorganics, which have long regarded as racemate. Here, we found lattice distortion reagents, assemblies were spontaneously organized during evaporation colloidal solution. These findings are likely to be phenomena that exist many substances drop hint studying chirality. 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Walter Lupton role particle morphology interfacial energy transfer CdSe/CdS heterostructure 330: 1371-1374Crossref (161) quantity introduced rods effective characterization. ?3.8 nm synthesized via hot-injection technique precursors, including wurtzite cores, trioctylphosphine (TOP), (TOPO), (TOPS), octadecylphosphoric acid (ODPA), n-hexylphosphonic (HPA), CdO (see experimental procedures section details). All proved pure (Figures S1 S2). wide-angle X-ray diffraction (XRD) pattern (Figure 1A) shows five major reflections 2? = 24.8°, 26.5°, 28.1°, 43.7°, 51.8°, assigned 101¯0, 0002, 101¯1, 112¯0, 112¯2 reflections, respectively, close-packing structure. Compared intensities reflection peaks bulk materials, 101¯0 112¯0 much stronger, while 0002 weaker, suggesting preferred orientation stack parallel substrate, further confirmed electron microscopy observations. solutions composed monodispersed single-crystalline average ?65 nm, shown transition (TEM) images 1B S3). detailed high-angle annular dark-field scanning transmission (HAADF-STEM) investigations. Figure 2A, energy-dispersive spectroscopy (EDS) linear scan showed (length 67 3.7 nm) uniform two sections CdSe. growth, cores size ?2.3 (determined Peng’s method,40Yu W.W. Guo Experimental determination extinction coefficient CdTe, CdSe, nanocrystals.Chem. 2854-2860Crossref (4614) S4) distributed 22 ? 25 40 48 regions nanorod. fine observed high-magnification HAADF-STEM image 2B), bright dot corresponds electrostatic potential area, namely, atoms. grain 2B mainly consists ABAB domains (blue 2B) bounded thin layers cubic ABCABC sequence (red phases blende, respectively. At boundary CdS/CdSe interface, determined EDS 2A), distorted arrangement observed, could mismatch lattice/basis fluctuation shaded areas 2B). worth noting continuous also this grain. A possible 3D model proposed explain observation, consisted intergrowth phase mixed zinc-blende 2D). connectivity S5. According model, contrast simulated image41Oleynikov eMap eSlice: software package crystallographic computing.Cryst. Res. Technol. 46: 569-579Crossref [112¯0]hex closely resembles results 2C). similarity comparing corresponding FDs (insets Figures This result suggests plausible structural characterized high-resolution TEM (HRTEM) [110]cub/[112¯0]hex direction, [111]cub/[0001]hex. Notably, only left part align zone axis, right region gradually tilted beam 3A1). Upon sequential left-handed tilting sample well-aligned (indicated red box) moved side 3A2–3A5). Fourier diffractograms (FDs) taken local positions judge alignment regions. right-handed approximate 6° rotation c over distance 72 angle ?0.08°/nm. Moreover, upon same S6), left-handedness feature found. reveal tried imaging single condition HCCN plane aligned highlighted. Initially, comparison conventional S7B1 S7A1). mark top-left corner S7A1, S7B2–S7B9), directly HCCN. addition, almost unchanged selected area patterns 9° indicate continuously understand HCCNs, change defect formation. Due heterogeneous composition protected], 3.8% expected {0001}hex planes phase, derived difference adjacent atoms layer (4.1365 Å 4.3000 CdSe). may interface. permanent dipole moment attraction cause merge, “oriented attachment” lowering total free suspension. If imperfect, it certain final products.42Tang Z.Y. Giersig organization CdTe luminescent nanowires.Science. 297: 237-240Crossref (1756) Scholar,43Nie Z.H. Petukhova Kumacheva Properties emerging applications self-assembled made nanoparticles.Nat. 15-25Crossref (1309) Scholar44Talapin Shevchenko Titov Kral Dipole?dipole interactions superlattices.Nano 2007; 1213-1219Crossref (292) noted above, nanocrystals original HCCNs. images, displayed 3B, viewed [1¯1¯1¯]cub/[0001¯]hex, three models show after relaxation (viewed [110]cub/[112¯0]hex, [211]cub/[101¯0]hex, perspective S8), obtained DMol3Soai program Materials Studio. translation [101¯0]hex operation (detailed modeling calculation S9–S13). translational operations subject restrictions within 5° 1.2 Å, considering requirements bond Cd-S (Tables 3Bi, atomic position bonding counterclockwise 3.2° perfect (gray colored below, [1¯1¯1¯]cub/[0001¯]hex direction). On hand, 5.6° 1.9° 3Bii 3Biii) criterion structure, energies ?83.48 ?83.19 eV, all ?83.47, ?83.24, indicating these thermodynamically stable (Table Thus, same. Similar clockwise CdS. 300°C evidenced samples different temperatures S14 S15). Both transmitted (CD) (CPL) spectra dispersed toluene solution silent signals, probably because racemate state too interaction selectivity light S16). significant purity smoothness quartz substrate examined XRD, (SEM), CD S17–S19). Smooth transparent simply facilely dropping subsequent evaporation. 4A absorbance (CCNFs) handedness. mirror-symmetrical CCNFs sharp negative peak centered ?466 shoulder ?430 ?380 relatively ?550 coinciding UV-vis bands. characteristic mechanism S20), include both absorption- scattering-based OAs. CCNFs, diffuse white background S21A) disappearance range 300–475 new 475–600 strong signals combination coupling OA (SOA) transition-based (ETOA). Bragg resonance optical air electronic states nanorods. black displays those spectra, confirming existence S21B), S22 S23). 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