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Blue Light Gives Way to Red

Photochemistry’s rise over the last ten years or so has been one of the big stories in organic chemistry, but there are still some difficulties with using it. The use of photoredox catalysts has brought blue light into a lot of fume hoods, which is certainly more selective and easier to use than than old ultraviolet sources – I will not miss mercury lamps, I can tell you. But the physical problem remains of getting enough photons poured into the reaction. It’s been demonstrated that with any of these sources that you only tend to get photoreactions in the outer few millimeters of the solution. Thus the flow photochemistry rigs that people have used, which are attempts to turn the entire reaction into a 2mm-deep layer around the light source – otherwise, you have to stir vigorously and just keep beaming away until things are finally done.

But physics to the rescue: there are other possibilities. Here’s a paper on one, triplet upconversion. Near-infrared light has far better ability to penetrate solutions (and tissue, for that matter). But taking advantage of that isn’t always easy. One of the reasons it’s penetrating is that it’s not be absorbed by anything along the way, and even when it is, light of those wavelengths isn’t packing enough energy to do a lot of work. It’s definitely not going to break or form any bonds by itself – absorption at those frequencies all goes into things like rotational or vibrational energy, so you’re just going to warm things up. And it’s not enough to send any of your favorite photoredox catalysts into an electronically excited state, either.

Triplet upconversion, though, is a way of pooling this energy and making something out of it. A sensitizer species is chosen that can usefully absorb the NIR light to provide a singlet excited state, and this decays to a triplet form. That interacts with another species (the “annihilator”), turning it into an excited triplet, and then two of those react with each other. One falls back to the ground state, and the other ends up boosted to yet a higher energy state, and then emits a photon with some oomph to it – you’ve upconverted near-IR light into the visible or even UV range by doing a two-for-one exchange. This is a big topic in many fields, not least solar energy production.

You have to pick your species carefully – the sensitizer, the annihilator, and eventual photoredox catalyst that absorbs that last photon – but what’s organic chemistry for if we can’t tune the properties of our molecules by changing their structures? This latest paper has gotten things to line up with a palladium octabutoxyphthalocyanine complex that absorbs down at 730nM, furanyldiketopyrrolopyrrole as the annhilator, and eosin as the eventual catalyst. Eosin is known to (for example) catalyze dehalogenation under blue-light conditions, and in this system it’ll do so under near-IR illumination. But you get comparable yields with the triplet-upconversion system while using a light source that’s only one-thousandth the power (!)

That’s because, physically, this would seem to be equivalent to setting off photochemical illumination sources, molecule-by-molecule, throughout most of the solution. Absorption tests showed that the NIR light was penetrating typical reaction solutions hundreds of times better than blue LED light, so that’s quite an improvement over trying to beat in the photons from the outside. Switching to a different (tetraphenyltetranaphthoporphyrin) palladium complex and a tetra-t-butylperylene annihilator (which emits up into the blue range), they were able to use the popular Ru(bpy)3 catalyst. Interestingly, in one of the systems tried (a cyclobutane-forming reaction), the catalyzed system gave a 48% yield, while leaving out the Ru catalyst still gave a 38% one, so it appears that the excited singlet perylene species is enough by itself to get the reaction to go in some cases.

This idea would seem to have real applications for photochemical scaleup. The higher penetration is a great feature, as is the lower power consumption, and the excess heat of whole setup would be a lot easier to deal with (it’s a major problem as you go to larger rigs). Getting your photons this way might be the photochemistry of the future, if enough good absorber/annihilator pairs can be identified.

17 comments on “Blue Light Gives Way to Red”

  1. Anon PChemist says:

    730nM should be 730 nm (nanometers, not nanomolar)

  2. a. nonymaus says:

    Upconversion is always a good time to be reminded of:
    https://www.youtube.com/watch?v=kTjfl0yhyRk

    That said, is this really easier than using a reactor that is ca. 2 absorption units thick? Leaves are leaf-shaped for a reason, and it isn’t just CO2 mass transfer.

    1. Doppler_chemist says:

      Well at least we know what the next 20 Science/Nature papers will look like โ€“ making the same products as the last 20 papers, just with red light instead of blue.

    2. eub says:

      It’s interesting that frequency-doubling apparently isn’t useful to photosynthesizers. But chlorophyll a already runs on red light, and for that matter some cyanobacteria stick antennas down into the IR.
      http://science.sciencemag.org/content/360/6394/1210

      Doubling would actually give photons too high in energy for your Photosystem I to know what to do with. I need to go read how the light harvesting systems “repackage” into to higher-energy photons. Apparently you can sum up excitons or something. Not that I understand Fรถrster resonance transfer [https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3098534/] at all in the first place.

  3. Rovislave says:

    Photoredox ๐Ÿ‘ killed ๐Ÿ‘ organic ๐Ÿ‘ chemistry ๐Ÿ‘

    1. Catalyser says:

      ๐Ÿ’๐Ÿผโ€โ™€๏ธ Someone needs to get their definition of organic chemistry UPCONVERTED

  4. AnonCoward says:

    “octabutoxyphthalocyanine” and “furanyldiketopyrrolopyrrole” sound like you had a fit on the keyboard ๐Ÿ™‚

    1. Olandese Volante says:

      “No, I didn’t type that with my elbows” (cit.)

  5. Nonchemist says:

    I’m sure this is obvious & been answered a million times… but wouldn’t it be easier to spread out the solution somehow to increase exposure surface area? ie: pour solution between two plates of glass with blue lights above & below. Spread it out, expose & react, gather up… rinse & repeat as necessary?

    1. milkshake says:

      coil some thin teflon tubing around a jar with LEDs inside

      1. Dionysius Rex says:

        I think that this is pretty much the custom rig that Enamine use – albeit a very large jam jar….

        1. Ivs says:

          Nope. Or sorta nope, really. The ones with a vertical coil of tubing have light sources outside the coil – because that way you can fit more lamps like that.
          But that’s the ones with low pressure UV lamps. The LED ones have flat coils lying under a large PCB with LEDs on it.

    2. Ivs says:

      It’s even easier done if you can run your reaction inside a spinning rotavap – set lamps above it, so they shine on that thin film smeared inside the flask.

      But, in general, if you are talking about going to continuous flow completely:
      1) some processes aren’t easy to convert to flow (say, something is a solid, or precipitates out),
      2) flow systems are harder to maintain,
      3) people may be just interested in chemistry more than in tinkering with equipment they might not have in the first place

    3. BK says:

      That is exactly what Derek mentioned; people using 3D printed flow paths to pump their reaction solution through it with a large enough light source to illuminate the entire flow path. The paths I’ve seen are around one square inch, so that is not hard to illuminate.

  6. Andy says:

    Scale up is a nightmare because of low penetration, even with a falling film reactor.

  7. ๐ŸŽบ says:

    Wow these desperate photo hacks will do anything to save FAILING photoredox. Don’t believe their parlor tricks people this whole field is FAKE SCIENCE. Build the pay wall and garbage science will fall!

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