Theor Chem Acc (2015) 134:116
1 3
signifi cant change in the overall pattern, i.e., also results
with WI basis are fairly reliable. The PCM model slightly
increased the calculated oscillator strengths, still preserving
the overall shape of the spectrum as in the gas phase.
In Fig. 6 , the predicted UV–Vis and ECD spectrum is
shown for the complex 1 . It is worth noting that due to the
mutual cancellation of rotatory strengths, the dichroism
apparently disappears in the range beyond ∼250 nm.
4.2.3 NMR spectra
Finally, let us briefl y comment on the calculated isotropic
NMR chemical shifts, as given in Table 4 . The
51 V NMR
chemical shifts were calculated using the GIAO approach
with well-established B3PW91 functional and the W-IGLO
basis set. These computations were performed employing optimized structures as defi ned in the fi rst column of
Table 4 . All chemical shifts are given with respect to the
VOCl 3 reference chemical shielding. Since PCM did not
provide any improvement, we just show in vacuo values.
A good agreement with experiment has been accomplished
for 2 and also for 3 . In 3 , the calculated values for V 1 and
V 2 are distinguished, unlike in experiment when a single
peak was observed. A rather big discrepancy with experiment in the case of 1 indicates relatively large deviation of
the calculated structure from the measured one in an aqueous solution. Similar differences were observed between
computed and experimental values for [VO 2 (H 2 O) 4 ] +
cation [ 28 ]. As for the performance of the employed geometries, even though the calculated chemical shifts vary
within about 10 % of their values, this is still acceptable.
5 Concluding remarks
A number of DFT calculations investigating the performance of a variety of functionals were performed for three
complex anions of vanadium(V) with tartrato ligands. As
expected, one can hardly fi nd a universal DFT method to
equally well describe structures together with the spectral
properties. Our further aim was to complement the experimentally available data for 1 , 2 , and 3 [ 16 , 17 ]. Hence, we
have confronted the results with those experiments. Structural parameters have been fairly well described using the
BP86 functional which can be safely recommended for further computations of a similar kind as a good compromise
between the cost-effectiveness and accuracy. Consequently,
the vibrational energy distribution analysis confi rmed and/
or complemented the measured spectral data.
Since the LMCT electronic transitions are dominant
in the electronic spectra, long-range corrected functionals have been employed in combination with the aforementioned optimized structures, CAM-B3LYP proving as
a favorite one. Calculated UV–Vis and ECD spectra were
confronted with the experimental recordings, performed
in this work for 3 , as well. This confrontation allowed to
reliably predict the pertinent spectra for 1 , where we were
unable to obtain ECD spectrum experimentally. Calculated
NMR chemical shifts were in good agreement with experiment for 2 and 3 , too.
Acknowledgments We thank Peter Schwendt for prompting this
work. JN appreciates a long-term friendship with Péter Surján whom
we dedicate this work on the occasion of his 60th birthday, and who
started his scientifi c carrier by calculating the rotatory strengths [ 64 ].
This work has been supported by the Grant Agency of the Ministry
of Education of the Slovak Republic and Slovak Academy of Sciences VEGA project no. 1/0336/13 as well as by the Slovak Research
and Development Agency (APVV-0510-12). Calculations were performed in the Computing Center of the Slovak Academy of Sciences
using the supercomputing infrastructure acquired in project ITMS
26230120002 and 26210120002 supported by the Research & Development Operational Programme funded by the ERDF.
Compliance with ethical standards
Confl ict of interest The authors declare that they have no confl ict
of interest.
References
1. Blair GT, DeFraties JJ (2000) Hydroxy dicarboxylic acids, kirk
othmer encyclopedia of chemical technology. Wiley, Hoboken, NJ
2. Williams ID, Pedersen SF, Sharpless KB, Lippard SJ (1984) J
Am Chem Soc 106:6340
3. Bryliakov KP, Talsi EP (2008) Curr Org Chem 12:386
4. Gan CS (2008) Can J Chem 86:261
5. Molnár P, Thorey P, Bánsághi G, Székely E, Poppe L, Tomin
A, Kemény EFS, Simándi B (2008) Tetrahedron Asymmetry
19:1587
6. Nakamura H, Fujii M, Sunatsuki Y, Kojima M, Matsumoto N
(2008) Eur J Inorg Chem 8:1258
7. Tapscott ER, Belford RL, Paul IC (1969) Coord Chem Rev 4:323
8. Nakazawa H, Yoneda H (1978) J Cromatogr 160:89
9. Wijeratne AB, Spencer SE, Gracia J, Armstrong DW, Schug KA
(2009) J Am Soc Mass Spectrom 20:2100
10. Sakurai H, Katoh A, Yoshikawa Y (2006) Bull Chem Soc Jpn
79:1645
11. Sakurai H, Kojima Y, Yoshikawa Y, Kawabe K, Yasui H (2002)
Coord Chem Rev 226:187
12. Sakurai H, Funakoshi S, Adachi Y (2005) Pure Appl Chem
77:1629
13. Murakami S, Habane S, Higashimura H (2007) Polymer 48:6565
14. Cortese AJ, Wilkins B, Smith MD, Yeon J, Morrison G, Tran TT,
Halasyamani PS, zur Loye HC (2015) Inorg Chem 54:4011
15. Antal P, Schwendt P, Tatiersky J, Gyepes R, Drábik M (2014)
Trans Metal Chem 39:893
16. Gáliková J, Schwendt P, Tatiersky J, Tracey AS, Žák Z (2009)
Inorg Chem 48:8423
17. Schwendt P, Tracey AS, Tatiersky J, Gáliková J, Žák Z (2007)
Inorg Chem 46:3971
18. Koch W, Holthausen MC (2002) A chemist’s guide to density
functional theory. Viley-VCH, Weinheim
19. Krivosudský L, Schwendt P, Šimunek J, Gyepes R (2014) Chem
Eur J 20:8872
131
Reprinted from the journal
1 3
signifi cant change in the overall pattern, i.e., also results
with WI basis are fairly reliable. The PCM model slightly
increased the calculated oscillator strengths, still preserving
the overall shape of the spectrum as in the gas phase.
In Fig. 6 , the predicted UV–Vis and ECD spectrum is
shown for the complex 1 . It is worth noting that due to the
mutual cancellation of rotatory strengths, the dichroism
apparently disappears in the range beyond ∼250 nm.
4.2.3 NMR spectra
Finally, let us briefl y comment on the calculated isotropic
NMR chemical shifts, as given in Table 4 . The
51 V NMR
chemical shifts were calculated using the GIAO approach
with well-established B3PW91 functional and the W-IGLO
basis set. These computations were performed employing optimized structures as defi ned in the fi rst column of
Table 4 . All chemical shifts are given with respect to the
VOCl 3 reference chemical shielding. Since PCM did not
provide any improvement, we just show in vacuo values.
A good agreement with experiment has been accomplished
for 2 and also for 3 . In 3 , the calculated values for V 1 and
V 2 are distinguished, unlike in experiment when a single
peak was observed. A rather big discrepancy with experiment in the case of 1 indicates relatively large deviation of
the calculated structure from the measured one in an aqueous solution. Similar differences were observed between
computed and experimental values for [VO 2 (H 2 O) 4 ] +
cation [ 28 ]. As for the performance of the employed geometries, even though the calculated chemical shifts vary
within about 10 % of their values, this is still acceptable.
5 Concluding remarks
A number of DFT calculations investigating the performance of a variety of functionals were performed for three
complex anions of vanadium(V) with tartrato ligands. As
expected, one can hardly fi nd a universal DFT method to
equally well describe structures together with the spectral
properties. Our further aim was to complement the experimentally available data for 1 , 2 , and 3 [ 16 , 17 ]. Hence, we
have confronted the results with those experiments. Structural parameters have been fairly well described using the
BP86 functional which can be safely recommended for further computations of a similar kind as a good compromise
between the cost-effectiveness and accuracy. Consequently,
the vibrational energy distribution analysis confi rmed and/
or complemented the measured spectral data.
Since the LMCT electronic transitions are dominant
in the electronic spectra, long-range corrected functionals have been employed in combination with the aforementioned optimized structures, CAM-B3LYP proving as
a favorite one. Calculated UV–Vis and ECD spectra were
confronted with the experimental recordings, performed
in this work for 3 , as well. This confrontation allowed to
reliably predict the pertinent spectra for 1 , where we were
unable to obtain ECD spectrum experimentally. Calculated
NMR chemical shifts were in good agreement with experiment for 2 and 3 , too.
Acknowledgments We thank Peter Schwendt for prompting this
work. JN appreciates a long-term friendship with Péter Surján whom
we dedicate this work on the occasion of his 60th birthday, and who
started his scientifi c carrier by calculating the rotatory strengths [ 64 ].
This work has been supported by the Grant Agency of the Ministry
of Education of the Slovak Republic and Slovak Academy of Sciences VEGA project no. 1/0336/13 as well as by the Slovak Research
and Development Agency (APVV-0510-12). Calculations were performed in the Computing Center of the Slovak Academy of Sciences
using the supercomputing infrastructure acquired in project ITMS
26230120002 and 26210120002 supported by the Research & Development Operational Programme funded by the ERDF.
Compliance with ethical standards
Confl ict of interest The authors declare that they have no confl ict
of interest.
References
1. Blair GT, DeFraties JJ (2000) Hydroxy dicarboxylic acids, kirk
othmer encyclopedia of chemical technology. Wiley, Hoboken, NJ
2. Williams ID, Pedersen SF, Sharpless KB, Lippard SJ (1984) J
Am Chem Soc 106:6340
3. Bryliakov KP, Talsi EP (2008) Curr Org Chem 12:386
4. Gan CS (2008) Can J Chem 86:261
5. Molnár P, Thorey P, Bánsághi G, Székely E, Poppe L, Tomin
A, Kemény EFS, Simándi B (2008) Tetrahedron Asymmetry
19:1587
6. Nakamura H, Fujii M, Sunatsuki Y, Kojima M, Matsumoto N
(2008) Eur J Inorg Chem 8:1258
7. Tapscott ER, Belford RL, Paul IC (1969) Coord Chem Rev 4:323
8. Nakazawa H, Yoneda H (1978) J Cromatogr 160:89
9. Wijeratne AB, Spencer SE, Gracia J, Armstrong DW, Schug KA
(2009) J Am Soc Mass Spectrom 20:2100
10. Sakurai H, Katoh A, Yoshikawa Y (2006) Bull Chem Soc Jpn
79:1645
11. Sakurai H, Kojima Y, Yoshikawa Y, Kawabe K, Yasui H (2002)
Coord Chem Rev 226:187
12. Sakurai H, Funakoshi S, Adachi Y (2005) Pure Appl Chem
77:1629
13. Murakami S, Habane S, Higashimura H (2007) Polymer 48:6565
14. Cortese AJ, Wilkins B, Smith MD, Yeon J, Morrison G, Tran TT,
Halasyamani PS, zur Loye HC (2015) Inorg Chem 54:4011
15. Antal P, Schwendt P, Tatiersky J, Gyepes R, Drábik M (2014)
Trans Metal Chem 39:893
16. Gáliková J, Schwendt P, Tatiersky J, Tracey AS, Žák Z (2009)
Inorg Chem 48:8423
17. Schwendt P, Tracey AS, Tatiersky J, Gáliková J, Žák Z (2007)
Inorg Chem 46:3971
18. Koch W, Holthausen MC (2002) A chemist’s guide to density
functional theory. Viley-VCH, Weinheim
19. Krivosudský L, Schwendt P, Šimunek J, Gyepes R (2014) Chem
Eur J 20:8872
131
Reprinted from the journal