Solar Energy Absorption in Norbornadiene

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system which increased the most by electron donating substituents (X = –NH2, –OH, and –CH3) attached at C2 (12 X), and/or electron withdrawing groups (X =.
ISSN 00360244, Russian Journal of Physical Chemistry A, 2011, Vol. 85, No. 5, pp. 814–818. © Pleiades Publishing, Ltd., 2011.

STRUCTURE OF MATTER AND QUANTUM CHEMISTRY

Solar Energy Absorption in Norbornadiene–Quadricyclane System through Electron Donating or Withdrawing Substituents1 L. Edjlalia, E. Vessallyb, and M. Abbasianc a

Islamic Azad University, Tabriz Branch, Tabriz, Iran b Payame Noor University, Zanjan, Iran c Payame Noor University, Tabriz, Iran email: [email protected] Received September 12, 2009

Abstract—An attempt is made to maximize the solar energy absorption in norbornadiene (1)–quadricyclane (2) system, through direct attachment of substituents at C1, C2 or C7 atoms of 1; calculating the correspond ing energies at B3LYP/6311++G** level of theory. The electron donating and electron withdrawing substit uents of 1nX, attached at C2, were suitable for both solar absorption bands and solar energy storage. DFT cal culations indicate that the solar absorption bands of 12X were shifted to the visible spectrum region through the electron withdrawing substituents more than through electron donating substituents. Keywords: solar energy, energy absorption, norbornadiene, quadricyclane, electron donating, electron with drawing. DOI: 10.1134/S0036024411050104 1

INTRODUCTION Norbornadiene (1)–quadricyclane (2) system is used for solar energy storage [1–3], in molecular switching [4–6], in optoelectronic devices [7–10], as a data storage compound [11, 12], as photodynamic chemosensor for metal cations, [13, 14] as a potential photoresponsive organic magnet [15–17] and as an energetic binder for solid rocket propellants [18]. This system has an inherent disadvantage that 1 cannot absorb visible wave length of sunlight. The donor– acceptor chromophores are placed at the double bond of the norbornadiene molecule. The water soluble car bamoyl and carboxyl derivatives of 1 and 2 are also used to absorb light of wavelengths longer than 300 nm [19]. Using of sensitizers and chromophores are two improvements to solve this problem. Iridium complex is proposed as the sensitizer for π–π* excitation [20]. Ab initio is used to study energetic of 1 and 2 conver sions [21, 22]. Density functional calculations with the hybrid B3LYP functional have been used to study the ground state of 1 bound to the photosensitizer [Cu(8 oxoquinolinato)] [23]. Follow up on our works [24– 28], in this manuscript we study the photochemical energy absorption in the ground states of 1–2 system with exchanging of substituents at C1, C2 or C7 atoms of 1. Storage of solar energy in nXnorbornadiene (1nX)–nXquadricyclane (2nX) system (where n = 1, 2 or 7 and X = –NO2, –CF3, –COOH, –COH, –CN,

1 The article is published in the original.

–F, –Cl, –Br, –H, –CH3, –OH and –NH2) is shown below: 7

8 X

1 6

2 3

4

5 (1nX)

hν

7

8 X

1 6

2 4 3

5 (2nX)

COMPUTATIONAL METHODS The molecular structures of nsubstituted norbor nadienes (1nX) and nsubstituted quadricyclanes (2nX) are studied using DFT methods. Geometry optimiza tions are carried out by B3LYP [29, 30] method using 6311++G** basis set of the Gaussian 98 system of program [31]. The B3LYP method was formed through a combination of the Becke’s three parameter hybrid functional and the LYP semilocal correlation functional. For all molecules under this study, all parameters such as geometry optimization, energies, vibrational frequencies, and thermodynamic charac teristics are calculated at B3LYB/6311++G** level of theory. In order to obtaining values of the electronic ener gies (E), enthalpies (H) and Gibbs free energies (G), “Freq” keyword is used. For calculations of the ther modynamic characteristics, the vibrational circular dichroism (VCD) intensities in addition to the normal frequency analysis were performed. Raman intensities

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815

Table 1. The B3LYP/6311++G*** calculated thermal energy separations (ΔE), enthalpy gaps (ΔH) and free energy split tings, (ΔG) in kcal mol–1, between nXnorbornadienes (1nX), and their corresponding nXquadricyclanes (2nX) X NO2 CF3 COOH COH CN F Cl Br H CH3 OH NH2

ΔE

ΔH

22.292 22.604 19.846 19.416 19.286 27.986 25.324 24.782 22.951 22.821 25.933 24.516

n=1 22.293 22.604 19.846 19.416 19.285 27.985 25.324 24.782 22.950 22.820 25.933 24.517

ΔG 25.463 23.027 21.373 19.671 19.503 28.452 25.822 25.292 23.537 23.284 26.484 24.682

ΔE

ΔH

21.039 21.359 22.107 20.863 23.124 24.084 23.277 22.871 22.951 23.676 26.429 26.755

n=2 21.040 21.359 22.107 20.863 23.125 24.085 23.277 22.872 22.950 23.677 26.429 26.755

in addition to IR intensities were also calculated. ReadIsotopes specified the alternate temperature, pressure, and/or isotopes. The analysis uses the stan dard expressions for an ideal gas in the canonical ensemble. The thermochemistry analysis treats all modes other than the free rotations and translations as harmonic vibrations. The Berny algorithm is employed for all minimizations using redundant inter nal coordinates [32]. Only real frequency values are accepted and the imaginary frequencies do not appear in the vibrational spectra of norbornadienes and quad ricyclanes. All calculations are carried out for gas phase at 298 K temperature and 1 atm pressure. The calculations exhibit systematic errors and thus benefit from scaling. Thermodynamic functions obtained through frequency calculations, are multi plied by 0.99 scaling factor of Rauhut and Pulay [33, 34] for B3LYP method. Scaling factors fitted to observe (anharmonic) frequencies will deviate from unity even for exact calculations [34]. Here, a set of molecules containing similar motifs are treated together, where they benefit from similar scalings. Simulation of UV/visspectra and their calculations are done by using SPARTAN program package [35]. The UV/Vis spectra is calculated by running TDDFT calculation after the main wavefunction has been cal culated. TDDFT calculation are done for the first excited state of optimized structures by 6311++G** basis set. RESULTS AND DISCUSSION Recently we have reported theoretical investiga tions on the electronic effects involved in the solar energy storage, for substituents “indirectly” attached to the C2 of 1 and/or 2, and “directly” attached at C1, C2 or C7 atoms of 1 and 2 [24, 28]. However, the solar RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

ΔG 21.919 22.121 22.754 21.198 23.456 24.715 23.901 23.492 23.537 24.442 26.928 27.446

ΔE

ΔH

ΔG

23.331 18.257 23.084 22.334 22.272 24.741 22.527 21.930 22.951 22.378 24.715 23.055

n=7 23.331 18.258 23.085 22.334 22.272 24.742 22.527 21.931 22.950 22.378 24.714 23.055

23.338 20.302 22.800 22.717 22.526 25.142 22.955 22.373 23.537 22.850 25.446 24.915

absorption bands of 1, which appear of “practical interest” to those whose primary goal is to replace the fossil fuel and/or the nuclear energy with the most economical and very available solar energy, have been not investigated. In this manuscript we study the solar absorption bands in the ground state of 1 with exchanging of substituents at C1, C2 or C7 of 1 and 2. Extend of the solar energy stored in this system is measured simply by calculation of the energy differ ence between the ground states of 1 and 2. Energy gaps between 1nX and 2nX have been calculated (Table 1) [28]. We have reported the solar energy storages in the system which increased the most by electron donating substituents (X = –NH2, –OH, and –CH3) attached at C2 (12X), and/or electron withdrawing groups (X = –NO2, –CF3, –COOH, –COH, –CN, –F, –Cl, ⎯Br) attached at C1 (12X) (Table 1). Again, energy gap and the extent of solar energy storage in 12X–22X sys tem is generally more than either 12X–21X and/or 17X–27X systems. Another words C2 is more sensitive to substituent effect than C1 and/or C7. However, the excited states of 1nX were not considered in the solar energy storage system for practical interest. The excited states of 1nX could be related to their corre sponding solar absorption bands. A chromophor or substituent was suitable for the solar energy storage system when the solar absorption band was shifted to the visible region. Therefore, in this manuscript, the effects of both electron withdrawing and electron donating substitu ents on solar absorption bands were investigated on various positions of 1nX and 2nX (X attached at carbons C1, C2 or C7: n = 1, 2 or 7, respectively). All the results of solar absorption bands for both electron withdrawing and electron donating substituents at C1, C2 or C7 of 1nX are tabulated by using Spartan pro gram (Table 2). In general, the spectral band position Vol. 85

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Table 2. Solar energy absorption wavelength (λ, nm) and their intensities (I) for optimized nXnorbornadienes (1nX) at B3LYP/6311++G** level by using Spartan program X

λ

I

λ

I

λ

NO2 CF3 COOH COH CN F Cl Br H CH3 OH NH2

215.8 189.7 208.2 217.3 189.7 192.0 198.0 204.8 204.3 205.0 203.0 217.2

0.009 0.000 0.002 0.014 0.001 0.000 0.002 0.004 0.001 0.001 0.045 0.009

244.1 192.8 216.5 230.2 193.6 196.5 199.4 207.5 208.8 211.0 205.2 219.4

0.001 0.002 0.020 0.016 0.020 0.002 0.007 0.002 0.000 0.015 0.003 0.004

259.0 196.0 218.5 234.9 194.0 198.8 201.7 215.6 209.6 215.6 216.1 225.1

NO2 CF3 COOH COH CN F Cl Br H CH3 OH NH2

205.5 186.8 200.4 205.2 197.3 204.0 204.5 207.1 204.3 212.8 218.8 231.4

0.016 0.017 0.125 0.179 0.065 0.004 0.006 0.007 0.001 0.014 0.004 0.007

217.9 191.1 203.8 213.1 198.4 206.2 206.9 210.0 208.8 217.2 227.0 243.0

0.059 0.006 0.059 0.009 0.037 0.014 0.024 0.027 0.000 0.013 0.007 0.0154

254 193.1 216.5 214.7 207.2 209.5 213.4 224.8 209.6 223.3 227.7 252.9

NO2 CF3 COOH COH CN F Cl Br H CH3 OH NH2

213.9 193.4 209.6 215.9 192.5 193.4 200.5 214.0 204.3 210.1 205.0 211.2

0.005 0.002 0.007 0.016 0.005 0.002 0.001 0.018 0.001 0.001 0.011 0.028

239.6 197.9 215.5 223.6 195.1 197.9 201.2 218.8 208.8 210.4 207.2 219.9

0.002 0.003 0.001 0.002 0.003 0.003 0.039 0.005 0.000 0.000 0.005 0.012

243.2 199.4 223.0 240.8 195.5 199.4 203.7 219.7 209.6 212.8 215.2 224.0

I n=1 0.016 0.014 0.000 0.001 0.002 0.015 0.001 0.000 0.017 0.001 0.008 0.036 n=2 0.156 0.006 0.010 0.013 0.019 0.002 0.005 0.007 0.017 0.004 0.004 0.004 n=7 0.002 0.016 0.003 0.003 0.007 0.016 0.004 0.001 0.017 0.018 0.012 0.022

in the absorption, reflectance, transmittance, or emis sion spectrum of a molecule is shifted to a longer wave length when a substituents was used at C1, C2 or C7 of 1nX. It was found that the electron donating and elec

λ

I

λ

I

λ

I

276.1 213.6 221.1 246.6 211.8 216.5 220.0 221.1 222.9 223.5 224.2 230.8

0.000 0.013 0.012 0.000 0.012 0.013 0.012 0.014 0.008 0.014 0.016 0.007

298.0 217.0 235.2 281.8 219.3 218.8 220.6 226.6 230.6 230.8 227.3 247.0

0.000 0.009 0.001 0.002 0.008 0.011 0.0144 0.007 0.013 0.012 0.011 0.004

326.0 244.5 246.0 304.0 245.0 244.5 245.4 241.8 248.2 251.3 249.0 252.2

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.003

294.6 210.9 234.5 234.7 213.4 218.4 228.0 231.9 222.9 223.8 244.9 263.9

0.007 0.013 0.064 0.103 0.007 0.008 0.010 0.018 0.008 0.004 0.006 0.007

321.6 218.3 262.7 302.6 235.6 227.7 229.0 241.3 230.6 241.7 270.2 289.1

0.015 0.012 0.013 0.017 0.052 0.010 0.006 0.005 0.013 0.005 0.003 0.012

356.0 253.4 294.1 347.1 277.7 249.3 255.4 262.3 248.2 252.3 279.0 301.6

0.008 0.001 0.012 0.000 0.011 0.000 0.006 0.008 0.000 0.002 0.001 0.001

302.3 216.6 227.0 248.5 215.1 216.6 218.0 220.6 222.9 223.8 219.1 231.1

0.000 0.016 0.009 0.006 0.012 0.016 0.007 0.014 0.008 0.006 0.008 0.021

309.2 216.6 247.7 271.7 223.0 216.6 219.2 228.8 230.6 232.2 232.5 242.0

0.001 0.008 0.006 0.001 0.011 0.008 0.009 0.005 0.013 0.018 0.013 0.020

352.8 243.8 273.9 321.2 254.7 243.8 248.8 250.8 248.2 251.6 246.2 251.8

0.001 0.001 0.000 0.001 0.000 0.001 0.000 0.000 0.000 0.000 0.001 0.019

tron withdrawing substituents of 1nX, attached at C2, properly shift the solar absorption bands to the longer wavelength in the visible spectrum region (Table 2). Electron donating and electron withdrawing substitu

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cate that the solar absorption bands of 12X were shifted to the visible spectrum region through the electron withdrawing substituents more than through electron donating substituents. The red shifts of solar absorp tion bands to the visible spectrum region through the electron withdrawing substituents are in the following order: 1 2NO2 > 12COH > 12COOH > 12CN > 1 2CF3 > 12H. The red shifts of solar absorption bands to the visible spectrum region through the electron donating and hologenated substituents are in the following order, respectively: 1 2NH2 > 12OH > 1 2CH3 > 12H and 12Br > 12 Cl > 12F ≥ 12H. The solar absorption bands of 12X, shifted to the visible spectrum region, is mainly attrib uted to the possibility of extention of conjugation of C=C by the attached substituents. For halogenated substituents of 12X, polarizability of Br atom leads to change the solar absorption bands to a longer wave length in the visible spectrum region.

Absorption X = withdrawing group

1

−NO2 −COH

0.01 −CN

0 200

−COOH

CF3

−H

0.0001

260

320

380

440

X = donating group

1

X = −NH2

0.01

817

X = −OH X = −H

0.0001 0 200

X = −CH2

260

320

380

440

1 0.01

X = −H X = −F

X = −Br X = −Cl

0.0001 0 200

260

320

380

440 λ, nm

Solar energy absorption for electron withdrawing, donat ing and halogenated substituents of norbornadienes (12X) at B3LYP/6311++G** level by using Spartan program; where X = –NO2, –CF3, –COOH, –COH, –CN, –F, – Cl, –Br, –H, –CH3, –OH and –NH2.

ents of 1nX, attached at C1, moderately induce solar absorption bands to the visible spectrum region. Therefore, the bathochromic shift or red shift of 1n X, are the most when the subsituents are attached at C2 carbon (n = 2), and the least when they are attached at C7 carbon atom (n = 7). These results for solar absorption bands are consis tent to calculated solar energy storage. Thus, the elec tron donating and electron withdrawing substituents of 1nX, attached at C2, were suitable for both solar absorption bands and solar energy storage. All the sub stituents attached at C2 were compared together and tabulated in figure and Table 2. DFT calculations indi RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

CONCLUSIONS The effects of both electron withdrawing and elec tron donating substituents are investigated on various positions of 1nX and 2nX. The electron donating and electron withdrawing substituents of 1nX, attached at C2, were suitable for both solar absorption bands and solar energy storage. DFT calculations indicate that the solar absorption bands of 12X were shifted to the visible spectrum region through the electron with drawing substituents more than through electron donating substituents. The red shifts through the elec tron withdrawing substituents are in the following order: 1 2NO2 > 12COH > 12COOH > 12CN > 1 2CF3 > 12H. The red shifts through the electron donating and hol ogenated substituents are in the following order, respectively: 1 2NH2 > 12OH > 1 2CH3 > 12H and 12Br > 12Cl > 12F ≥ 12H. ACKNOWLEDGMENTS Islamic Azad University, Tabriz Branch is gratefully acknowledged due to their financial support (Grant) of this research. REFERENCES 1. R. R. Hautala, R. B. King, and C. Kutal, Solar Energy: Chemical Conversion and Storage (Hummana, Clifton, NJ, 1979), P. 333. 2. V. A. Bren, A. D. Dubonosov, V. I. Minkin, and V. A. Chernoivanov, Russ. Chem. Rev. 60, 451 (1991). 3. A. Cox, Photochemistry 30, 389 (1999). 4. P. Laine, V. Marvaud, A. Gourdon, J. P. Launnay, R. Argazzi, and C. A. Bignozzi, Inorg. Chem. 35, 711 (1996). 5. E. E. Bonfantini and D. L. Officer, J. Chem. Soc. Chem. Commun., 1445 (1994). Vol. 85

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