A dual functional nanohybrid object combining photonic and magnetic properties was successfully prepared through a “bottom-up” self-assembly approach. In this method, spin transition Fe(II) coordination nanoparticles and optical wave guiding organic nanorods were generated in situ and successfully integrated together in a single pot through self-assembly. The Fe(II) nanoparticles coated on organic nanorods (nanohybrids) display temperature dependent reversible spin transition (Paramagnetic; diamagnetic; ) behavior. The nano-hybrids show efficient optical wave guiding behavior, which demonstrates the future possibility to perform light induced excited spin state trapping (LIESST) experiments on a single spin transition nanoparticle level. These photonic and magnetic “nanohybrids” offer promising option to externally manipulate spin state of the spin transition nanoparticles using temperature as well as remote laser light. 1. Introduction Bottom-up nanofabrication of self-assembled multifunctional nanoobjects and study of their uncharted physical properties at the nanoscale level are an active and sophisticated research area of nanoscience and technology [1–13]. Particularly programming the in situ growth of self-assembled organic and inorganic nanostructures from different molecular components and also their integration to form hybrid nanoscale objects in the same pot is a less explored area. A successful groundwork in this discipline might lead to new advanced functional hybrid nanomaterials capable of performing a sensing, electronic, photonic, and mechanical function [1–13]. For example integration of magnetically bistable inorganic nanoparticles (NPs) and optical wave guiding organic nanostructures could facilitate remote manipulation of the light sensitive spin states of individual NPs through guided laser light. Recently, we have reported for the first time on the passive wave guiding behavior of organic tubes and also demonstrated the remote electronic excitation of a mesotetratolylporphyrin nanosheet using a 20？ m long optical wave guiding organic tube [14–16]. Hence we intended to study the propensity of the 1D organic solids coated with spin transition NPs [17–37] (ST-NPs) to guide source laser light under laser confocal microscope setup. It was anticipated that the dielectric difference between the 1D nano-hybrid solid and the surrounding medium would guide the optical wave along the growth axis of the waveguide. Among NPs, Fe(II) ST-NPs are of interest due to their switchable bistable magnetic spin states between paramagnetic high-spin state
References
[1]
S. Mann, “Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions,” Nature Materials, vol. 8, pp. 781–792, 2009.
[2]
C. A. Mirkin and C. M. Niemeyer, Nanobiotechnology II, Wiley-VCH, Weinheim, Germany, 2007.
[3]
C. A. Mirkin, R. L. Letsinger, R. C. Mucic, and J. J. Storhoff, “A DNA-based method for rationally assembling nanoparticles into macroscopic materials,” Nature, vol. 382, no. 6592, pp. 607–609, 1996.
[4]
E. Katz and I. Willner, “Integrated nanoparticle-biomolecule hybrid systems: synthesis, properties, and applications,” Angewandte Chemie International Edition, vol. 43, pp. 6042–6108, 2004.
[5]
T. Nakanishi, “Supramolecular soft and hard materials based on self-assembly algorithms of alkyl-conjugated fullerenes,” Chemical Communications, vol. 46, no. 20, pp. 3425–3436, 2010.
[6]
K. J. C. van Bommel, A. Friggeri, and S. Shinkai, “Organic templates for the generation of inorganic materials,” Angewandte Chemie International Edition, vol. 42, no. 9, pp. 980–999, 2003.
[7]
M. Li, C. Viravaidya, and S. Mann, “Polymer-mediated synthesis of ferritin-encapsulated inorganic nanoparticles,” Small, vol. 3, no. 9, pp. 1477–1481, 2007.
[8]
M. Okuda, Y. Kobayashi, K. Suzuki et al., “Self-organized inorganic nanoparticle arrays on protein lattices,” Nano Letters, vol. 5, no. 5, pp. 991–993, 2005.
[9]
P. J. Meadows, E. Dujardin, S. R. Hall, and S. Mann, “Template-directed synthesis of silica-coated j-aggregate nanotapes,” Chemical Communications, no. 29, pp. 3688–3690, 2005.
[10]
A. J. Patil, M. Li, E. Dujardin, and S. Mann, “Novel bioinorganic nanostructures based on mesolamellar intercalation or single-molecule wrapping of DNA using organoclay building blocks,” Nano Letters, vol. 7, no. 9, pp. 2660–2665, 2007.
[11]
M. Sofos, J. Goldberger, D. A. Stone et al., “A synergistic assembly of nanoscale lamellar photoconductor hybrids,” Nature Materials, vol. 8, no. 1, pp. 68–75, 2009.
[12]
N. Chandrasekhar and R. Chandrasekar, “Engineering self-assembled fluorescent organic nanotapes and submicrotubes from n-conjugated molecules,” Chemical Communications, vol. 46, no. 17, pp. 2915–2917, 2010.
[13]
S. Basak and R. Chandrasekar, “Multiluminescent hybrid organic/inorganic nanotubular structures: one-pot fabrication of tricolor (Blue Red-Purple) luminescent parallepipedic organic superstructure grafted with europium complexes,” Advanced Functional Materials, vol. 21, no. 4, pp. 667–673, 2011.
[14]
N. Chandrasekhar, M. A. Mohiddon, and R. Chandrasekar, “Organic submicro tubular optical waveguides: self-assembly, diverse geometries, efficiency, and remote sensing properties,” Advanced Optical Materials, vol. 1, no. 4, pp. 305–311, 2013.
[15]
P. Hui and R. Chandrasekar, “Light propagation in high-spin organic microtubes self-assembled from shape persistent macrocycles carrying oxo-verdazyl biradicals,” Advanced Materials, vol. 25, no. 21, pp. 2963–2967, 2013.
[16]
N. Chandrasekhar and R. Chandrasekar, “Reversibly shape-shifting organic optical waveguides: formation of organic nanorings, nanotubes, and nanosheets,” Angewandte Chemie International Editio, vol. 51, no. 15, pp. 3556–3561, 2012.
[17]
P. Gütlich and H. A. Goodwin, Eds., Spin Crossover in Transition Metal Compounds I, vol. 233 of Topics in Current Chemistry, Springer, Berlin, Germany, 2004.
[18]
H. Spiering, Spin Crossover in Transition Metal Compounds III, vol. 235 of Topics in Current Chemistry, Springer, Berlin, Germany, 2004.
[19]
E. K？nig, “Structural changes accompanying continuous and discontinuous spin-state transitions,” in Progress in Inorganic Chemistry, vol. 35, p. 527, 1987.
[20]
A. B. Gaspar, V. Ksenofontov, M. Seredyuk, and P. Gütlich, “Multifunctionality in spin crossover materials,” Coordination Chemistry Reviews, vol. 249, no. 23, pp. 2661–2676, 2005.
[21]
P. Gütlich, Y. Garcia, and T. Woike, “Photoswitchable coordination compounds,” Coordination Chemistry Reviews, vol. 219–221, pp. 839–879, 2001.
[22]
M. A. Halcrow, “Iron(II) complexes of 2,6-di(pyrazol-1-yl)pyridines—a versatile system for spin-crossover research,” Coordination Chemistry Reviews, vol. 253, no. 21-22, pp. 2493–2514, 2009.
[23]
T. Forestier, S. Mornet, N. Daro et al., “Nanoparticles of iron(II) spin-crossover,” Chemical Communications, no. 36, pp. 4327–4329, 2008.
[24]
E. Coronado, J. R. Galán-Mascarós, M. Monrabal-Capilla, J. Garca-Martnez, and P. Pardo-Ibá？ez, “Bistable spin-crossover nanoparticles showing magnetic thermal hysteresis near room temperature,” Advanced Materials, vol. 19, pp. 1359–1361, 2007.
[25]
F. Volatron, L. Catala, E. Rivière, A. Gloter, O. Stéphan, and T. Mallah, “Spin-crossover coordination nanoparticles,” Inorganic Chemistry, vol. 47, no. 15, pp. 6584–6586, 2008.
[26]
I. Boldog, A. B. Gaspar, V. Martinez et al., “Spin-crossover nanocrystals with magnetic, optical, and structural bistability near room temperature,” Angewandte Chemie International Edition, vol. 47, no. 34, pp. 6433–6437, 2008.
[27]
J. Larionova, L. Salmon, Y. Guari et al., “Towards the ultimate size limit of the memory effect in spin-crossover solids,” Angewandte Chemie International Edition, vol. 47, no. 43, pp. 8236–8240, 2008.
[28]
J.-F. Létard, “Photomagnetism of iron(II) spin crossover complexes-the T(LIESST) approach,” Journal of Materials Chemistry, vol. 16, pp. 2550–2559, 2006.
[29]
R. Chandrasekar, F. Schramm, O. Fuhr, and M. Ruben, “An iron(II) spin-transition compound with thiol anchoring groups,” European Journal of Inorganic Chemistry, no. 17, pp. 2649–2653, 2008.
[30]
M. Cavallini, I. Bergenti, S. Milita et al., “Micro and nanopatterning of spin-transition compounds into logical structures,” Angewandte Chemie International Edition, vol. 47, no. 45, pp. 8596–8600, 2008.
[31]
C. Rajadurai, F. Schramm, S. Brink et al., “Spin transition in a chainlike supramolecular iron(II) complex,” Inorganic Chemistry, vol. 45, no. 25, pp. 10019–10021, 2006.
[32]
C. Rajadurai, O. Fuhr, R. Kruk, M. Ghafari, H. Hahn, and M. Ruben, “Above room temperature spin transition in a metallo-supramolecular coordination oligomer/polymer,” Chemical Communications, no. 25, pp. 2636–2638, 2007.
[33]
C. Rajadurai, Z. Qu, O. Fuhr et al., “Lattice-solvent controlled spin transitions in iron(ii) complexes,” Dalton Transactions, no. 32, pp. 3531–3537, 2007.
[34]
N. Chandrasekhar and R. Chandrasekar, “‘Super hybrid tridentate ligands’: 4-substituted-2-(1-butyl-1H-1,2,3-triazol-4-yl)-6-(1H-pyrazol-1-yl)pyridine ligands coordinated to Fe(ii) ions display above room temperature spin transitions,” Dalton Transactions, vol. 39, no. 41, pp. 9872–9878, 2010.
[35]
S. Basak, P. Hui, and R. Chandrasekar, “Flexible and optically transparent polymer embedded nano/micro scale spin crossover Fe(II) complex patterns/arrays,” Chemistry of Materials, vol. 25, no. 17, pp. 3408–3413, 2013.
[36]
I. Salitros, J. Pavlik, R. Boca, O. Fuhr, C. Rajadurai, and M. Ruben, “Supramolecular lattice-solvent control of iron(ii) spin transition parameters,” Crystal Engineering Communications, vol. 12, no. 8, pp. 2361–2368, 2010.
[37]
R. Gonzalez-Prieto, B. Fleury, F. Schramm et al., “Tuning the spin-transition properties of pyrene-decorated 2,6-bispyrazolylpyridine based Fe(ii) complexes,” Dalton Transactions, vol. 40, no. 29, pp. 7564–7570, 2011.
[38]
N. Chandrasekhar and R. Chandrasekar, “‘Click-fluors’: synthesis of a family of π-conjugated fluorescent back-to-back coupled 2,6-bis(triazol-1-yl)pyridines and their self-assembly studies,” Journal of Organic Chemistry, vol. 75, pp. 4852–4855, 2010.
[39]
S. Basak, P. Hui, S. Boodida, and R. Chandrasekar, “Micropatterning of metallopolymers: syntheses of back-to-back coupled octylated 2,6-Bis(pyrazolyl)pyridine ligands and their solution-processable coordination polymers,” Journal of Organic Chemistry, vol. 77, no. 7, pp. 3620–3626, 2012.
[40]
S. Vaucher, M. Li, and S. Mann, “Synthesis of prussian blue nanoparticles and nanocrystal superlattices in reverse microemulsion,” Angewandte Chemie International Edition, vol. 39, no. 10, pp. 1793–1796, 2000.
[41]
P. Chakraborty, M. L. Boillot, A. Tissot, and A. Hauser, “Photoinduced relaxation dynamics in iron(ii) spin-crossover nanoparticles: the significance of crystallinity,” Angewandte Chemie International Edition, vol. 52, no. 1, p. 1, 2013.
[42]
S. Decurtins, P. Gütlich, C. P. K？hler, and H. Spiering, “New examples of light-induced excited spin state trapping (liesst) in iron(ii) spin-crossover systems,” Journal of the Chemical Society, Chemical Communications, no. 7, pp. 430–432, 1985.
[43]
J.-F. Létard, P. Guionneau, L. Rabardel et al., “Structural, magnetic, and photomagnetic studies of a mononuclear iron(II) derivative exhibiting an exceptionally abrupt spin transition. light-induced thermal hysteresis phenomenon,” Inorganic Chemistry, vol. 37, no. 17, pp. 4432–4441, 1998.
[44]
N. O. Moussa, E. Trzop, S. Mouri et al., “Wavelength selective light-induced magnetic effects in the binuclear spin crossover compound {[Fe(bt)(NCS)2]2(bpym)},” Physical Review B, vol. 75, no. 5, Article ID 054101, 2007.
