第9回分子科学討論会, 2015年9月16日-19日, 東京工業大学大岡山キャンパス(東京), 1A1

Ebata, Takayuki

Hirai, Kenta

Inokuchi, Yoshiya

Kida, Motoki

Soga, Kazuki

Name not available

金属イオン－カリックスアレーン錯体の極低温気相レーザー分光

第9回分子科学討論会, 2015年9月16日-19日, 東京工業大学大岡山キャンパス(東京

Hiroshima University Institutional Repository

金属イオンーカリックスアレーン錯体の 極低温気相レーザー分光 （広大院理）	○井口佳哉，曽我和毅，平井健太， 木田　基，江幡孝之	Outline 1. Introduction Why ion guest-host complexes? Why cold gas-phase spectroscopy?   2. Construction of instrument Estimation of Tion by UVPD spectroscopy  3. Application to ion complexes K+•calix[4]arene complex Electronic and geometric structure  4. Future prospectsGuest selectivity of hosts in water, 298 K M+   +   DB18C6     M+•DB18C6KDB18C6Izatt et al., Chem. Rev., 	85, 271 (1985).  Relation between K, ΔG, ΔH, and ΔS K = exp −ΔGRT#$%&'(ΔG = ΔH −TΔSComplex properties reflect selectivity? EnergyΔGΔGStructure? Isomers? guesthostCold gas-phase spectroscopy is useful M+M+•benzo-18-crown-6 (M+•B18C6) Tvib = ~10 KInokuchi et al., J. Phys. Chem. A, 116, 4057 (2012).Li+Na+K+Rb+Cs+Bare C4Asharp vibronic bands           conformer-specific experimentThis study• Construction of instrument Estimation of Tion by UVPD spectroscopy   • Application to ion complexes K+•calix[4]arene complex Electronic and geometric structure UV photodissociation spectroscopy dissociationUVEnergyS0 S1 UV WavenumberIntensity of + ++UV photodissociation spectroscopy He cryostatESIPaul trap OPIG potential switchMCPgate electrodeUVskimmercapillary Laser spectroscopy with cold quadrupole Paul trap Jouvet, Zwier, Johnson, Kim, Grégoire, Ishiuchi (3P014)…Ions in cold Paul trap are not so cold?aChoi et al., Chem. Phys. Lett., 593, 150 (2014).Collisional activation (heating) of ions in RF ion trap?Paul trap (~10 K)a Tvib = 50 K36050 36150 3625022-pole trap (~6 K)b Tvib = ~10 KbInokuchi et al., J. Phys. Chem. A, 116, 4057 (2012).K+•B18C6 hot band Ions can be cooled to ~10 K even in Paul trapFragment Ion IntensityUV Wavenumber (cm–1)K+•B18C6 Paul trap (~6.5 K)b Tvib = 35 K22-pole trap (~6 K)a Tvib = ~10 KPaul trap (~4.3 K)b Tvib = ~10 KaInokuchi et al., J. Phys. Chem. A, 116, 4057 (2012).bInokuchi et al., J. Phys. Chem. A, 119, 8512 (2015).Calix[4]arene (C4A) Four phenols are connected by –CH2– chains. Four OH groups form a rigid H-bonded ring.Ikeda and Shinkai, Chem. Rev., 97, 1713 (1997).   Ebata et al., J. Chem. Phys., 126, 141101 (2007).K+•C4A shows sharp UV bands Fragment Ion IntensityUV Wavenumber (cm–1)K+•C4A 3601836156 36515Inokuchi et al., J. Phys. Chem. A, 119, 8512 (2015).Isomers of K+•C4AKC4A-IKC4A-IIKC4A-IIIendo exo +97 kJ/mol exo +101 kJ/mol Gaussian09 M05-2X/6-31+G(d)K+ ion shifts the UV band to the blue 3601835357K+•C4A bare C4AEbata et al., J. Chem. Phys., 126, 141101 (2007).UV spectra are similar for K+•C4A and C4ARelative UV Wavenumber (cm–1)K+•C4A C4AWeak origin band, followed by strong bands.KC4A-I reproduces UVPD spectrum K+•C4A UVPD C4A LIFC4AKC4A-IKC4A-IIKC4A-IIIS1 S1 S1 S1 S2, S3 S3 S2 Gaussian09 M05-2X/6-31+G(d), S.F. = 0.843C4A and K+•C4A have high symmetry S0 (A) C4AS1 (A) S2, S3 (E) (C4 sym.)  K+•C4A S0 (A) S1 (A) S2 (B) S3 (B) (C2 sym.) 1Lb C4A and K+•C4A have high symmetry Relative UV Wavenumber (cm–1)S1 (A) K+•C4A C4AS1 (A) S2 (B)  S3 (B) S2, S3 (E) C4A in K+•C4A is highly distorted 34.1˚34.1˚6.83 Å33.2˚37.0˚bare C4AH2O•C4A 55.7˚13.2˚5.77 Å 7.63 ÅK+•C4A Future prospects■Cold gas-phase spectroscopy Host-guest complexes Organometallic complexes Hypervalent compounds■SEIRA spectroscopy on metal surfaceIRO OOOOOOSAuOO OO OIROSAu15C5-C1OC6 18C6-C1OC6log(K D–1 / M–1)543210–1–2Na+ K+ Rb+ Cs+Li+M+•15C5-C1OC6 in waterM+•18C6-C1OC6 in waterInokuchi et al., J. Phys. Chem. A, 119, 8512 (2015).Inokuchi et al., Chem. Phys. Lett., 592, 90 (2014). Inokuchi et al., New J. Chem., 2015, DOI: 10.1039/c5nj01787d .  Na+•15C5-C1OC6 in waterIR Wavenumber (cm–1)DAbsorbance (10–3 )ΔSummary■　We have constructed a mass spectrometer for UVPD spectroscopy with a cold, quadrupole Paul ion trap.  ■　We have estimated Tvib in the trap to be ~10 K by the UVPD spectrum of K+•B18C6.    ■　The UVPD spectrum of K+•C4A was measured; it shows sharp vibronic bands.  ■　The spectral features and theoretical results suggest that K+•C4A has an endo form with C2 symmetry.  

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金属イオン－カリックスアレーン錯体の極低温気相レーザー分光

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